4-trifluoromethyl-3-oxazolylpyridines, processes for their preparation, compositions comprising them and their use as pesticides

ABSTRACT

Compounds of the formula:                    
     wherein R 1 , R 2 , and m are as defined herein, and compositions comprising them, which are suitable for controlling animal pests.

The invention relates to 4-trifluoromethyl-3-oxazolylpyridines, to processes for their preparation, to compositions comprising them and to their use for controlling animal pests, in particular insects, spider mites, ectoparasites and helminths.

It is already known that suitably substituted pyridines have acaricidal and insecticidal action. Thus, WO 95/07891 discloses pyridines which carry, in the 4 position, a cycloalkyl radical which is attached via a heteroatom and, in the 3 position, a group of various substituents. However, the desired action with respect to harmful organisms is not always satisfactory. Additionally, these compounds frequently have undesirable toxicological properties with respect to mammals and aquatic animals.

International Application WO-A-98/57969, which is no prior publication, proposes 4-haloalkyl-3-heterocyclylpyridines and -pyrimidines for use as pesticides.

It was an object of the present invention to provide compounds having good insecticidal and acaricidal properties, combined with low toxicity with respect to mammals and aquatic animals.

It has now been found that compounds of the formula (I), if desired also as salts, have, compared with the prior-art compounds, a broader activity spectrum with respect to animal pests, combined with more favorable toxicological properties with respect to mammals and aquatic animals.

Accordingly, the invention provides compounds of the formula (I),

where the symbols and indices are as defined below:

m is 0 or 1;

R¹ and R² are

a) H, CH₃, —C₂H₅, —CH₂—CH₂—CH₃, —CH₂(CH₃)₂ or cyclopropyl or

b) —CH₃, —CH₂XR³, —CHY, —CO₂R⁴ or —CONR⁵R⁶,

where in each case one of the radicals R¹, R² is of the group a and the other is of the group b;

X is O, S, SO, SO₂ or NR⁷;

Y is O, BR₂, —O—(CH₂)₂—O—, ((C₁-C₄)-alkoxy)₂, ((C₁-C₄)-alkylthio)₂, V—(CH₂)₂ or ₃—V, where V=O, S, where an H atom is optionally replaced by (C₁-C₄) alkyl;

R³ is R⁸, COR⁹, CO₂R¹⁰, CONR¹¹R¹² or, if X is O or NR⁷, SO₂R¹³,

R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³ are identical or different and are independently of one another H, (C₁-C₁₀)-alkyl, (C₂-C₁₀)-alkenyl, (C₂-C₁₀)-alkynyl, (C₃-C₈)-cycloalkyl, (C₄-C₈)-cycloalkenyl, (C₆-C₈)-cycloalkynyl, aryl or heterocyclyl, where each of the eight last-mentioned groups is unsubstituted or mono- or polysubstituted, and where, if appropriate, in each case R⁵ and R⁶ and R¹¹ and R¹² together are —(CH₂)₄—, —(CH₂)₅—, —(CH₂)₂—O—(CH₂)₂— or —(CH₂)₂—NR⁴—(CH₂)₂;

with the proviso, that the compounds in which

R¹=CO₂C₂H₅ and R²=H,

R¹=H and R²=CH₂ NHC₆H₅,

R¹=CH₃ and R²=CO₂H,

R¹=CH₃ and R²=CO₂C₂H₅,

R¹=CH₃ and R²=CON(CH₃)₂,

R¹=CH(CH₃)₂ and R²=CO₂H,

R¹=CH(CH₃)₂ and R²=CO₂C₂H₅ are not included.

Preferred compounds of the formula (I) are, for example,

1. compounds in which R¹ is H and R² is a radical of the group b;

2. compounds in which R¹ is a radical of the group b and R² is H,

3. compounds in which R¹ is a radical of the group a, with the exception of hydrogen, and R² is a radical of the group b.

m is preferably 0.

If m=1 and R¹ or R²=CH₂S(O)_(n)R³, n is preferably 2.

From the group a, H, CH₃ and cyclopropyl are preferred. From the group b, CH₂XR³ and —CONR⁵R⁶ are preferred.

R^(4 . . . 13) are preferably

a) H, (C₁-C₁₀)-alkyl, (C₂-C₁₀)-alkenyl, (C₂-C₁₀)-alkynyl, (C₃-C₈)-cycloalkyl, (C₄-C₈)-cycloalkenyl, (C₆-C₈)-cycloalkynyl, where the six last-mentioned radicals are unsubstituted or substituted by one or more radicals from the group consisting of:

halogen, cyano, citro, hydroxyl, —C(═W)R¹⁴, —C(═NOR¹⁰)R¹⁴, —C(═NNR¹⁴ ₂)R¹⁴, —C(═W)OR¹⁴, —C(═W)NR¹⁴ ₂, —OC(═W)R¹⁴, —OC(═W)OR¹⁴, —NR⁵C(═W)R¹⁴, —N[C(═W)R¹⁴]₂, —NR¹⁴C(═W)OR¹⁴, —C(═W)NR¹⁴—NR¹⁴ ₂, —C(═W)NR¹⁴—NR¹⁴[C(═W)R¹⁵], —NR¹⁴—C(═W)NR¹⁴ ₂, —NR¹⁴—NR¹⁴C(═W)R¹⁴, —NR¹⁴—N[C(═W)R¹⁴]₂, —N[(C═W)R¹⁴]—NR¹⁴ ₂, —NR¹⁴—NR¹⁴[(C═W)WR¹⁴], —NR¹⁴(C═NR¹⁴)R¹⁴, —NR¹⁴(C═NR¹⁴)—NR¹⁴ ₂, —O—NR¹⁴ ₂, —O—NR¹⁴(C═W)R¹⁴, —SO₂NR¹⁴ ₂, —NR¹⁴SO₂R¹⁴, —SO₂OR¹⁴, —OSO₂R¹⁴, —OR¹⁴, —NR¹⁴ ₂, —SR¹⁴, —SiR¹⁴ ₃, —SeR¹⁴, —PR¹⁴ ₂, —P(═W)R¹⁴ ₂, —SOR¹⁴, —SO₂R¹⁴, —PW₂R¹⁴ ₂, —PW₃R¹⁴ ₂, aryl and

heterocyclyl,

the two last-mentioned radicals of which are unsubstituted or substituted by one or more radicals from the group consisting of

(C₁-C₆)-alkyl, (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl, (C₃-C₈)-cycloalkyl, (C₄-C₈)-cycloalkenyl, (C₆-C₈)-cycloalkynyl, (C₁-C₆)-haloalkyl, (C₂-C₆)-haloalkenyl, (C₂-C₆)-haloalkynyl, halogen, —OR¹⁴, —NR¹⁴ ₂, —SR¹⁴, —SiR¹⁴ ₃, —C(═W)R¹⁴, —C(═W)OR¹⁴, —C(═W)NR¹⁴ ₂, —SOR¹⁴, —SO₂R¹⁴, nitro, cyano and hydroxyl,

b) aryl, which is unsubstituted or substituted by one or more radicals from the group consisting of (C₁-C₆)-alkyl, (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl, (C₃-C₈)-cycloalkyl, (C₄-C₈)-cycloalkenyl and (C₆-C₈)-cycloalkynyl, where these six abovementioned radicals are unsubstituted or substituted by one or more radicals from the group consisting of

halogen, cyano, nitro, —C(═W(R¹⁴, —C(═W)OR¹⁴, —C(═W)NR¹⁴ ₂, —OR¹⁴, —NR¹⁴ ₂, —SR¹⁴, —SOR¹⁴ and —SO₂R¹⁴, halogen, cyano, nitro, —C(═W)R¹⁴, —C═NOR¹⁰)R¹⁴, —C(═NNR¹⁴ ₂)R¹⁴, —C(═W)OR¹⁴, —C(═W)NR¹⁴ ₂, —OC((═W)R¹⁴, —OC(═W)OR¹⁴, —NR¹⁴C(═W)R¹⁴, —[C(═W)R¹⁴]₂, —NR¹⁴C(═W)OR¹⁴, —OR¹⁴, —NR¹⁴ ₂, —SR¹⁴, —SiR¹⁴ ₃, —PR¹⁴ ₂, —SOR¹⁴, —SO₂R¹⁴, —PW₂R¹⁴ ₂ and —PW₃R¹⁴ ₂,

c) heterocyclyl which is unsubstituted or substituted by one or more radicals from the group consisting of

(C₁-C₆)-alkyl, (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl, (C₃-C₈)-cycloalkyl, (C₄-C₈)-cycloalkenyl and (C₆-C₈)-cycloalkynyl,

where these six abovementioned radicals are unsubstituted or substituted by one or more radicals from the group consisting of

halogen, cyano, nitro, —C(═W)R¹⁴, —C(═W)OR¹⁴, —C(═W)NR¹⁴ ₂), OR¹⁴, —NR¹⁴ ₂, —SR¹⁴, —SOR¹⁴ and —SO₃R¹⁴,

halogen, cyano, nitro, —C(═W(R¹⁴, —C(═NOR¹⁰)R¹⁴, —C(═NNR¹⁴ ₂)R¹⁴, —C(═W)OR¹⁴, —C(═W)NR¹⁴ ₂, —OC(═W)R¹⁴, —OC(═W)OR¹⁴, —NR¹⁴C(═W)R¹⁴, —[C(═W)R¹⁴]₂, —NR¹⁴C(═W)OR¹⁴, —OR¹⁴—NR¹⁴ ₂, —SR¹⁴, SiR¹⁴ ₃, —PR¹⁴ ₂, —SOR¹⁴, —SO₂R¹⁴, —PW₂R¹⁴ and —PW₃R¹⁴ ₂,

W is O or S;

R¹⁴ is identical or different and is hydrogen, (C₁-C₆)-alkyl, (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl, (C₃-C₈)-cycloalkyl, (C₄-(C₈)-cycloalkenyl, (C₃-C₈)-cycloalkyl-(C₁-C₄)-alkyl, (C₄-C₈)-cycloalkenyl-(C₁-C₄)alkyl, (C₃-C₈)-cycloalkyl-(C₂-C₄)alkenyl, (C₄-C₈)-cycloalkenyl-(C₁-C₄)-alkenyl, (C₁-C₆)-alkyl-(C₃-C₈)-cycloalkyl, (C₂-C₆)-alkenyl-(C₃-C₈)-cycloalkyl, (C₂-C₆)-alkynyl-(C₃-C₈)-cycloalkyl, (C₁-C₆)-alkyl-(C₄-C₈)-cycloalkenyl, (C₂-C₆)-alkenyl-(C₄-C₈)cycloalkenyl, where the fourteen last-mentioned radicals are unsubstituted or substituted by one or more, preferably 1 to 3, radicals from the group consisting of

halogen, cyano, nitro, hydroxyl, thio, amino, formyl, (C₁-C₆)-alkoxy, (C₂-C₆)-alkenyloxy, (C₂-C₆)-alkynyloxy, (C₁-C₆)-haloalkyloxy, (C₂-C₆)-haloalkenyloxy, (C₂-C₆)-haloalkynyloxy, (C₃-C₈)-cycloalkoxy, (C₄-C₈)-cycloalkenyloxy, (C₃-C₈)-halocycloalkoxy, (C₄-C₈)-halocycloalkenyloxy, (C₃-C₈)-cycloalkyl-(C₁-C₄)-alkoxy, (C₄-C₈)-cycloalkenyl-(C₁-C₄)-alkoxy, (C₃-C₈)-cycloalkyl-(C₂-C₄)-alkenyloxy, (C₄-C₈)-cycloalkenyl-(C₁-C₄)-alkenyloxy, (C₁-C₆)-alkyl-(C₃-C₈)-cycloalkoxy, (C₂-C₆)-alkenyl-(C₃-C₈)-cycloalkoxy, (C₂-C₆)-alkynyl-(C₃-C₈)-cycloalkoxy, (C₁-C₆)-alkyl-(C₄-C₈)-cycloalkenyloxy, (C₂-C₆)-alkenyl-(C₄-C₈)-cycloalkenyloxy, (C₁-C₄)-alkoxy-(C₁-C₆)-alkoxy, (C₁-C₄)-alkoxy-(C₂-C₆)-alkenyloxy, carbamoyl, (C₁-C₆)-mono- or -dialkylcarbamoyl, (C₁-C₆)-mono- or dihaloalkylcarbamoyl, (C₃-C₈)-mono- or dicycloalkylcarbamoyl, (C₁-C₆)-alkoxycarbonyl, (C₃-C₈)-cycloalkoxycarbonyl, (C₁-C₆)-alkanoyloxy, (C₃-C₈)-cycloalkanoyloxy, (C₁C₆)-haloalkoxycarbonyl, (C₁-C₆)-haloalkanoyloxy, (C₁-C₆)-alkanamido, (C₁-C₆)-haloalkanamido, (C₂-C₆)-alkanamido, (C₃-C₈)-cycloalkanamido, (C₃-C₈)-cycloalkyl-(C₁-C₄)-alkanamido, (C₁-C₆)-alkylthio, (C₂-C₆)-alkenylthio, (C₂-C₆)-alkynylthio, (C₁-C₆)-haloalkylthio, (C₂-C₆)-haloalkenylthio, (C₂-C₆)-haloalkynylthio, (C₃-C₈)-cycloalkylthio, (C₄-C₈)-cycloalkenylthio, (C₃-C₈)-halocycloalkylthio, (C₄-C₈)-halocycloalkenyllthio, (C₃-C₈)-cycloalkyl-(C₁-C₄)-alkylthio, (C₄-C₈)cycloalkenyl-(C₁-C₄)-alkylthio, (C₃-C₈)-cycloalkyl-(C₂-C₄)-alkenylthio, (C₄-C₈)-cycloalkenyl-(C₁-C₄)-alkenylthio, (C₁-C₆)-alkyl-(C₃-C₈)-cycloalkylthio, (C₂-C₆)-alkenyl-(C₃-C₈)-cycloalkylthio, (C₂-C₆)-alkynyl-(C₃-C₈)-cycloalkylthio, (C₁-C₆)-alkyl-(C₄-C₈)-cycloalkenylthio, (C₂-C₆)-alkenyl-(C₄-C₈)-cycloalkenylthio, (C₁-C₆)-alkylsulfinyl, (C₂-C₆)-alkenylsulfinyl, (C₂-C₆)-alkoynylsulfinyl, (C₁-C₆)-haloalkylsulfinyl, (C₂-C₆)-haloalkenylsulfinyl, (C₂-C₆)-haloalkynylsulfinyl, (C₃-C₈)-cycloalkylsulfinyl, (C₄-C₈)-cycloalkenylsulfinyl, (C₃-C₈)-halocycloalkylsulfinyl, (C₄-C₈)-halocycloalkenylsulfinyl, (C₃-C₈)-cycloalkyl-(C₁-C₄)-alkylsulfinyl, (C₄-C₈)-cycloalkenyl-(C₁-C₄)-alkylsulfinyl, (C₃-C₈)-cycloalkyl-(C₂-C₄)-alkenylsulfinyl, (C₄-C₈)-cycloalkenyl-(C₁-C₄)-alkenylsulfinyl, (C₁-C₆)-alkyl-(C₃-C₈)-cycloalkylsulfinyl, (C₂-C₆)-alkenyl-(C₃-C₈)-cycloalkylsulfinyl, (C₂-C₆)-alkynyl-(C₃-C₈)-cycloalkylsulfinyl, (C₁-C₆)-alkyl-(C₄-C₈)-cycloalkenylsulfinyl, (C₂-C₆)-alkenyl-(C₄-C₈)-cycloalkenylsulfinyl, (C₁-C₆)-alkylsulfonyl, (C₂-C₆)-alkenylsulfonyl,

(C₂-C₆)-alkynylsulfonyl, (C₁-C₆)-haloalkylsulfonyl, (C₂-C₆)-haloalkenylsulfonyl, (C₂-C₆)-haloalkynylsulfonyl, (C₃-C₈)-cycloalkylsulfonyl, (C₄-C₈)-cycloalkenylsulfonyl, (C₃-C₈)-halocycloalkylsulfonyl, (C₄-C₈) -halocycloalkenylsulfonyl, (C₃-C₈)-cycloalkyl-(C₁-C₄)-alkylsulfonyl, (C₄-C₈)-cycloalkenyl-(C₁-C₄)-alkylsulfonyl, (C₃-C₈)-cycloalkyl-(C₂-C₄)-alkenylsulfonyl, (C₄-C₈)-cycloalkenyl-(C₁-C₄)-alkenylsulfonyl, (C₁-C₆)-alkyl-(C₃-C₈)-cycloalkylsulfonyl, (C₂-C₆)-alkenyl-(C₃-C₈)-cycloalkylsulfonyl, (C₂-C₆)-alkynyl-(C₃-C₈)-cycloalkylsulfonyl, (C₁-C₆)-alkyl-(C₄-C₈)-cycloalkenylsulfonyl, (C₂-C₆)-alkenyl-(C₄-C₈)-cycloalkenylsulfonyl, (C₁-C₆)-alkylamino, (C₂-C₆)-alkenylamino, (C₂-C₆)-alkynylamino, (C₁-C₆)-haloalkylamino, (C₂-C₆)-haloalkenylamino, (C₂-C₆)-haloalkynylamino, (C₃-C₈)-cycloalkylamino, (C₄-C₈)-cycloalkenylamino, (C₃-C₈)-halocycloalkylamino, (C₄-C₈)-halocycloalkenylamino, (C₃-C₈)-cycloalkyl-(C₁-C₄)-alkylamino, (C₄-C₈)-cycloalkenyl-(C₁-C₄)-alkylamino, (C₃-C₈)-cycloalkyl-(C₂-C₄)-alkenylamino, (C₄-C₈)-cycloalkenyl-(C₁-C₄)-alkenylamino, (C₁-C₆)-alkyl-(C₃-C₈)-cycloalkylamino, (C₂-C₆)-alkenyl-(C₃-C₈)-cycloalkylamino, (C₂-C₆)-alkynyl-(C₃-C₈)-cycloalkylamino, (C₁-C₆)-alkyl-(C₄-C₈)-cycloalkenylamino, (C₂-C₆)-alkenyl-(C₄-C₈)-cycloalkenylamino, (C₁-C₆)-trialkylsilyl, aryl, aryloxy, arylthio, arylamino, aryl-(C₁-C₄)-alkoxy, aryl-(C₂-C₄)-alkenyloxy, aryl-(C₁-C₄)-alkylthio, aryl-(C₂-C₄)-alkenylthio, aryl-(C₁-C₄)-alkylamino, aryl-(C₂-C₄)-alkenylamino, aryl-(C₁-C₆)-dialkylsilyl, diaryl-(C₁-C₆)-alkylsilyl, triarylsilyl and 5- or 6-membered heterocyclyl, where the cyclic moiety of the fourteen last-mentioned radicals is unsubstituted or substituted by one or more radicals from the group consisting of

halogen, cyano, nitro, amino, hydroxyl, thio, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₃-C₈)-cycloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthio, (C₁-C₄)-haloalkylthio, (C₁-C₄)-alkylamino, (C₁C₄)-haloalkylamino formyl and (Cl-C₄)-alkanoyl,

aryl, 5- or 6-membered heteroaromatic, where the two last-mentioned radicals are unsubstituted or substituted by one or more radicals from the group consisting of

halogen, cyano, nitro, hydroxyl, thio, amino, formyl, (C₁-C₆)-alkoxy, (C₂-C₆)-alkenyloxy, (C₂-C₆)-alkynyloxy, (C₁-C₆)-haloalkyloxy, (C₂-C₆)-haloalkenyloxy, (C₂-C₆)-haloalkynyloxy, (C₃-C₈)-cycloalkoxy, (C₄-C₈)-cycloalkenyloxy, (C₃-C₈)-halocycloalkoxy, (C₄-C₈)-halocycloalkenyloxy, carbamoyl, (C₁-C₆)-mono- or -dialkylcarbamoyl, (C₁-C₆)-alkoxycarbonyl, (C₁-C₆)-alkanoyloxy, (C₁-C₆)-mono- or -dihaloalkylcarbamoyl, (C₁-C₆)-haloalkoxycarbonyl, (C₁-C₆)-haloalkanoyloxy, (C₁-C₆)-alkanamido, (C1-C₆)-haloalkanamido, (C₂-C₆)-alkanamido, (C₁-C₆)-alkylthio, (C₂-C₆)-alkenylthio, (C₂-C₆)-alkynylthio, (C₁-C₆)-haloalkylthio, (C₂-C₆)-haloalkenylthio, (C₂-C₆)-haloalkynylthio, (C₃-C₈)-cycloalkylthio, (C₄-C₈)-cycloalkenylthio, (C₃-C₈)-halocycloalkylthio, (C₄-C₈)-halocycloalkenylthio, (C₁-C₆)-alkylsulfinyl, (C₂-C₆)-alkenylsulfinyl, (C₂-C₆)-alkynylsulfinyl, (C₁-C₆)-haloalkylsulfinyl, (C₂-C₆)-haloalkenylsulfinyl, (C₂-C₆)-haloalkynylsulfinyl, (C₃-C₈)-cycloalkylsulfinyl, (C₄-C₈)-cycloalkenylsulfinyl, (C₃-C₈)-halocycloalkylsulfinyl, (C₄-C₈)-halocycloalkenylsulfinyl, (C₁-C₆)-alkylsulfonyl, (C₂-C₆)-alkenylsulfonyl, (C₂-C₆)-alkynylsulfonyl, (C₁-C₆)-haloalkylsulfonyl, (C₂-C₆)-haloalkenylsulfonyl, (C₂-C₆)-haloalkynylsulfonyl, (C₃-C₈)-cycloalkylsulfonyl, (C₄-C₈)-cycloalkenylsulfonyl, (C₃-C₈)-halocycloalkylsulfonyl, (C₄-C₈)-halocycloalkenylsulfonyl, (C₁-C₆)-alkylamino, (C₂-C₆)-alkenylamino, (C₂-C₆)-alkynylamino, (C₁-C₆)-haloalkylamino, (C₂-C₆)-haloalkenylamino, (C₂-C₆)-haloalkynylamino, (C₃-C₈)-cycloalkylamino, (C₄-C₈)-cycloalkenylamino, (C₃-C₈)-halocycloalkylamino and (C₄-C₈)-halocycloalkenylamino.

R^(4 . . . 14) are particularly preferably identical or different and are H, (C₁-C₆)-alkyl, (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl, (C₃-C₆)-cycloalkyl, (C₄-C₆)-cycloalkenyl, aryl or heterocyclyl, where each of the seven last-mentioned groups is unsubstituted or substituted by one or more radicals from the group consisting of halogen, preferably F, (C₁-C₄)-alkoxy, (C₁-C₄)-alkylthio, NR′—CO—(C₁-C₆)-alkyl, where R′=H or (C₁-C₄)-alkyl.

Particular preference is given to the following groups of compounds of the formula (I) a-f

Very particular preference is given to compounds of the formula Ia1-Ia12

Very particular preference is furthermore given to compounds of the formula 1b1 to 1b12:

The symbols in the formulae Ia-f and 1a-12, respectively, and Ib1-12 have the abovementioned meanings and preferences.

The term “halogen” includes fluorine, chlorine, bromine and iodine.

The term “(C₁-C₄)-alkyl” is to be understood as a straight-chain or branched hydrocarbon radical having 1, 2, 3 or 4 carbon atoms, such as, for example, the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl radical. Correspondingly, alkyl radicals having a greater range of carbon atoms are to be understood as straight-chain or branched saturated hydrocarbon radicals which contain a number of carbon atoms which corresponds to the range stated. Thus, the term “(C₁-C₆)-alkyl” includes the abovementioned alkyl radicals, and, for example, the pentyl, 2-methylbutyl, 1,1-dimethylpropyl, hexyl radical. The term “(C₁-C₁₀)-alkyl” is to be understood as the abovementioned alkyl radicals, and, for example, the nonyl, 1-decyl or 2decyl radical.

“(C₁-C₄)-Haloalkyl” is to be understood as an alkyl group mentioned under the term “(C₁-C₄)-alkyl” in which one or more hydrogen atoms are replaced by the same number of identical or different halogen atoms, preferably chlorine or fluorine, such as, for example, the trifluoromethyl, the 1-fluoroethyl, the 2,2,2-trifluoroethyl, the chloromethyl, fluoromethyl, the difluoromethyl and the 1,1,2,2-tetrafluoroethyl group.

“(C₁-C₄)-Alkoxy” is to be understood as an alkoxy group whose hydrocarbon radical has the meaning given under the term “(C₁-C₄)-alkyl”. The alkoxy groups embracing a greater range of carbon atoms are to be understood correspondingly.

The terms “alkenyl” and “alkynyl” having a prefix stating the range of carbon atoms denote a straight-chain or branched hydrocarbon radical having a number of carbon atoms corresponding to the range stated which comprises at least one multiple bond which may be in any position of the unsaturated radical in question. “(C₂-C₄)-Alkenyl” is thus, for example, the vinyl, allyl, 2-methyl-2-propenyl or 2-butenyl group; “(C₂-C₆)-alkenyl” denotes the abovementioned radicals and, for example, the pentenyl, 2-methylpentenyl or the hexenyl group. “(C₂-C₄)-Alkynyl” is, for example, the ethynyl, propargyl, 2-methyl-2-propynyl or 2-butynyl group. “(C₂-C₆)-Alkynyl” is to be understood as the abovementioned radicals and, for example, the 2-pentynyl or the 2-hexynyl group and “(C₂-C₁₀)-alkynyl” is to be understood as the abovementioned radicals and, for example, the 2-octynyl or the 2-decynyl group.

“(C₃-C₈)-Cycloalkyl” denotes monocyclic alkyl radicals, such as the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl radical and bicyclic alkyl radicals, such as the norbornyl radical.

The term “(C₃-C₈)-cycloalkyl-(C₁-C₄)-alkyl ” is to be understood as, for example, the cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclohexylethyl and cyclohexylbutyl radical, and the term “(C₁-C₆)-alkyl-(C₃-C₈)-cycloalkyl is to be understood as, for example, the 1-methylcyclopropyl, 1-methylcyclopentyl, 1-methylcyclohexyl, 3-hexylcyclobutyl and 4-tert-butyl-cyclohexyl radical.

“(C₁-C₄)Alkoxy-(C₁-C₆)-alkyloxy” is an alkoxy group as defined above which is substituted by a further alkoxy group, such as, for example, 1-ethoxyethoxy.

“(C₃-C₈)-Cycloalkoxy” or “(C₃-C₈)-cycloalkylthio” is to be understood as one of the abovementioned (C₃-C₈)-cycloalkyl radicals which is linked via an oxygen or sulfur atom.

“(C₃-C₈)Cycloalkyl-(C₁-C₆)-alkoxy” is, for example, the cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclohexylethoxy or the cyclohexylbutoxy group.

The term “(C₁-C₄)-alkyl-(C₃-C₈)-cycloalkoxy” is, for example, the methylcyclopropyloxy, methylcyclobutyloxy or the butylcyclohexyloxy group.

“(C₁-C₆)-Alkylthio” is an alkylthio group whose hydrocarbon radical has the meaning given under the term “(C₁-C₆)-alkyl”.

Correspondingly, “(C₁-C₆)-alkylsulfinyl” is, for example, the methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl-, sec-butyl- or tert-butylsulfinyl group and “(C₁-C₆)-alkylsulfonyl” is, for example, the methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl-, sec-butyl- or tert-butylsulfonyl group.

“(C₁-C₆)-Alkylamino” is a nitrogen atom which is substituted by one or two identical or different alkyl radicals of the above definition.

The term “(C₁-C₆)-mono- or -dialkylcarbamoyl” is a carbamoyl group having one or two hydrocarbon radicals which have the meaning given under the term “(C₁-C₆-alkyl)” and which, in the case of two hydrocarbon radicals, may be identical or different.

Correspondingly, “(C₁-C₆)-dihaloalkylcarbamoyl” is a carbamoyl group which carries two (C₁-C₆)-haloalkyl radicals in accordance with the above definition or one (C₁-C₆)-haloalkyl radical and one (C₁-C₆)-alkyl radical in accordance with the above definition.

“(C₁-C₆)-Alkanoyl” is, for example, the acetyl, propionyl, butyryl or 2-methylbutyryl group.

The term “aryl” is to be understood as an carbocyclic aromatic radical preferably having 6 to 14, in particular 6 to 12, carbon atoms, for example phenyl, naphthyl or biphenylyl, preferably phenyl.

The term “heterocyclyl” preferably denotes a cyclic radical which may be fully saturated, partially unsaturated or fully unsaturated and which may be interrupted by at least one or more identical or different atoms from the group consisting of nitrogen, sulfur or oxygen, two oxygen atoms, however, not being allowed to be directly adjacent to one another and at least one carbon atom having to be present in the ring, for example a thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,3,4-triazole, 1,2,4-oxadiazole, 1,2,4-thiadiazole, 1,2,4-triazole, 1,2,3-triazole, 1,2,3,4-tetrazole, benzo[b]thiophene, benzo[b]furan, indole, benzo[c]thiophene, benzo[c]furan, isoindole, benzoxazole, benzothiazole, benzimidazole, benzisoxazole, benzisothiazole, benzopyrazole, benzothiadiazole, benzotriazole, dibenzofuran, dibenzothiophene, carbazole, pyridine, pyrazine, pyrimidine, pyridazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,5-triazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, 1,8-naphthyridine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, phthalazine, pyridopyrimidine, purine, pteridine, 4H-quinolizine; piperidine, pyrrolidine, oxazoline, tetrahydrofuran, tetrahydropyran, isoxazolidine or thiazolidine radical. The term “heteroaromatic” thus embraces, from among the meanings mentioned above under “heterocyclyl”, in each case the fully unsaturated aromatic heterocyclic compounds.

Heterocyclyl is particularly preferably a saturated, partially saturated or aromatic ring system having 3 to 6 ring members and 1 to 4 heteroatoms from the group consisting of O, S and N.

Heterocyclyl is very particularly preferably a radical of pyridine, pyrimidine, (1,2,4)-oxadiazole, (1,3,4)-oxadiazole, pyrrole, furan, thiophene, oxazole, thiazole, imidazole, pyrazole, isoxazole, 1,2,4-triazole, tetrazole, pyrazine, pyridazine, oxazoline, thiazoline, tetrahydrofuran, tetrahydropyran, morpholine, piperidine, piperazine, pyrroline, pyrrolidine, oxazolidine, thiazolidine, oxirane and oxetane.

“Aryl-(C₁-C₄)-alkoxy” is an aryl radical which is attached via a (C₁-C₄)-alkoxy group, for example the benzyloxy, phenylethoxy, phenylbutoxy or naphthylmethoxy radical. “Arylthio” is an aryl radical attached via a sulfur atom, for example the phenylthio or the 1- or 2-naphthylthio radical. Correspondingly, “aryloxy” is, for example, the phenoxy or 1- or 2-naphthyloxy radical.

“Aryl-(C₁-C₄)-alkylthio” is an aryl radical which is attached via an alkylthio radical, for example the benzylthio, naphthylmethylthio or the phenylethylthio radical.

The term “(C₁-C₆)-trialkylsilyl” denotes a silicon atom which carries three identical or different alkyl radicals in accordance with the above definition. Correspondingly “aryl-(C₁-C₆)-dialkylsilyl” is a silicon atom which carries one aryl radical and two identical or different alkyl radicals in accordance with the above definition, “diaryl-(C₁-C₆)-alkylsilyl” is a silicon atom which carries one alkyl radical and two identical or different aryl radicals in accordance with the above definition, and “triarylsilyl” is a silicon atom which carries three identical or different aryl radicals in accordance with the above definition.

Depending on the nature of the substituents defined above, the compounds of the formula (I) have acidic or basic properties and can form salts. If the compounds of the formula (I) carry, for example, groups such as hydroxyl, carboxyl or other groups inducing acidic properties, these compounds can be reacted with bases to give salts. Suitable bases are, for example, hydroxides, carbonates, bicarbonates of the alkali metals and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, further ammonia, primary, secondary and tertiary amines having (C₁-C₄)-alkyl radicals and also mono-, di- and trialkanolamines of (C₁-C₄)-alkanols. If the compounds of the formula (I) carry, for example, groups such as amino, alkylamino or other groups inducing basic properties, these compounds can be reacted with acids to give salts. Suitable acids are, for example, mineral acids, such as hydrochloric acid and sulfuric acid and phosphoric acid, organic acids, such as acetic acid and oxalic acid and acidic salts, such as NaHSO₄ and KHSO₄. The salts which can be obtained in this manner likewise have insecticidal, acaricidal and nematicidal properties.

The compounds of the formula (I) may have one or more asymmetric carbon atoms or stereoisomers on double bonds. Enantiomers or diastereomers may therefore be present. The invention embraces both the pure isomers and mixtures thereof. The mixtures of diastereomers can be separated into the isomers by customary methods, for example by selective crystallization from suitable solvents or by chromatography. Racemates can be separated into the enantiomers by customary methods. The compounds according to the invention are prepared according to methods which are known per se from the literature, as described in standard works on organic synthesis, for example Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart.

The preparation is carried out under reaction conditions which are known and suitable for the reactions mentioned. It is also possible to employ variants which are known per se but not mentioned in more detail here.

If desired, the starting materials can also be formed in situ, such that they are not isolated from the reaction mixture but are immediately reacted further to give the compounds of the formula (I).

The present invention also relates to processes for preparing compounds of the formula (I):

Compounds of the formula (I) where R²=H can be prepared, for example, by further functionalization of compound (III) or (IV):

The compounds (III) and (IV) are obtained, for example, by cyclizing compounds of the formula (V):

Various cyclization procedures are known from the literature, for example

KOH/ethanol/reflux (see, for example, J. Reisch et al., Pharmazie 1992, 47, 18-20)

NaH/THF/70° C. (see, for example, B. M. Nilsson et al., J. Heterocyclic Chem. 1989, 26, 269-275)

Hg (CH₃CO₂)2/glacial acetic acid/reflux (see, for example, J. Saunders et al., J. Med. Chem. 1990, 33, 1128-1130).

The starting material (V) is directly obtainable from commercially available trifluoromethylnicotinic acid and propargylamine by employing a dehydrating agent, such as dicyclohexylcarbodiimide, 1-ethyl-3-(3-di-methylaminopropyl)carbodiimide or N,N′-carbonyldiimidazole.

Compounds of the formula (I) where R¹=H can be obtained, for example, by further functionalization of the compound (VI)

Compound (VI) can be prepared, for example, in two steps by cyclization of (VII):

where (VII) is, for example, initially treated at 40° C. in glycol dimethyl ether with trimethylsilyl trifluoromethylsulfonate, followed by treatment with potassium tert-butoxide in tert-butanol at 0° C. to give (VI) (see, for example, S. Swaminathan et al., Tetrahedron Lett. 1998, 39, 4769-4472).

Compound (VII) can be prepared, for example, under standard conditions by acylating ethyl 2-amino-3,3,diethoxypropionate with 4-trifluoromethyl-nicotinoyl chloride. Ethyl 2-amino-3,3-diethoxypropionate can be prepared by processes known from the literature (see, for example, S. K. Singh et al., Heterocycles 1997, 44, 379-391 or T. W. Doyle et al., Can. J. Chem. 1977, 55, 468-483).

Compounds in which R¹ is a radical of the group a and R² is of the group b can be prepared, for example, by further functionalization of compounds of the formula (VIII):

where

R¹⁵ is CH₃ or C₂H₅ and

R¹⁶ is CH₃, C₂H₅, CH₂—CH₂—CH₃, —CH(CH₃)₂ or cyclopropyl.

(VIII) can be prepared, for example, by cyclizing amides of the formula (IX).

Suitable dehydrating agents which can be used for this purpose are, for example, inorganic acid chlorides, such as thionyl chloride or phosphoryl chloride, inorganic acids, such as sulfuric acid or phosphoric acid, or a mixture of acetic anhydride with an inorganic acid (see, for example, K. Meguro et al., Chem. Pharm. Buul.1986, 34, 2840-2851).

The compounds of formula (IX) can be prepared, for example, in a one-pot process from the corresponding β-ketoester (X) and 4-trifluoromethylnicotinoyl chloride.

The preparation of the oxime from the β-ketoester with sodium nitrite in acetic acid, reduction with Zn/sulfuric acid and subsequent acylation is described, for example, in G. Erhart, Berichte 1949, 82, 60-63.

After the oxazole system has been constructed by condensation and cyclization reactions, the radicals R¹ and R² of the compounds of the formula (XL) can, if desired, be derivatized further, using the broad range of methods of organochemical synthesis familiar to the person skilled in the art.

Esters and carboxamides of the formula (I) can be obtained, for example, from compounds of the formula (XI) by methods known from the literature and familiar to the person skilled in the art, such as transesterification, aminolysis or amide formation from carboxylic acids and amines using a dehydrating agent, such as dicyclohexylcarbodiimide, 1-ethyl-3-(3-di-methylaminopropyl)carbodiimide, N,N′-carbonyldiimidazole or 2-(1H-benzotriazol-2-yl)-1,1,3,3-tetramethylammonium tetrafluoroborate.

where

R¹, R² or R^(1′), R^(2′) have, for example, the following meanings:

R¹ = H; R² = CO₂H R^(1′) = H; R^(2′) = CO₂R⁴, CONR⁵R⁶ R¹ = CO₂Et, CO₂H; R² = H R^(1′) = CO₂R⁴, CONR⁵R⁶; R^(2′) = H R¹ = CO₂Me, CO₂Et, CO₂H R^(1′) = CO₂R⁴, CONR⁵R⁶, R² = Me, Et, n-Pr, i-Pr and c-Pr R^(2′) = Me, Et, i-Pr and c-Pr (c = cyclo).

R⁴, R⁵ and R⁶ are as defined above.

Compounds of formula (XI) where R¹=CO₂Et, CO₂Me, CO₂H; R²=H, Me, Et, n-Pr, i-Pr and c-Pr can be obtained directly by the cyclization reactions described or by hydrolysis of the esters of cyclization products.

Compound (XI) where R¹=H and R²=CO₂H can be prepared, for example, from compound (III) or (IV) by oxidation according to processes known from the literature.

Ethers, thioethers and amines and other derivatives of the formula (XIV) can be obtained, for example, from compounds of the formula (XIII) by reactions with appropriate nucleophiles, said reactions being known from the literature and familiar to the person skilled in the art.

where X, R³ and R⁴ are as defined above.

Compounds of the formula (XIII) can be prepared from compounds of the formulae (III), (VI) and (VIII) by processes which are known from the literature and familiar to the person skilled in the art, for example

Compounds of the formula (XIV) in which R¹ or R² is CH₂XR³ where X=S or NR⁴, where R³ or R⁴=H or R³=R⁴=H can be reacted by methods known from the literature and familiar to the person skilled in the art to give, for example, sulfoxides, sulfones, amides and carbamates.

To synthesize compounds of the formula (I) in which m is 1, it is possible to treat compounds of the formula (I) in which m is 0 with an oxidizing agent, such as meta-chloroperbenzoic acid.

Collections of compounds of the formula (I) which can be synthesized by the abovementioned scheme may also be prepared in a parallel manner and this may be effected manually or in a semiautomated or fully automated manner. In this case, it is possible, for example, to automate the procedure of the reaction, the work-up or the purification of the products or of the intermediates. In total, this is to be understood as meaning a procedure as is described, for example, by S. H. DeWitt in “Annual Reports in Combinatorial Chemistry and Molecular Diversity: Automated synthesis”, Volume 1, Verlag Escom 1997, pages 69 to 77.

A number of commercially available apparatuses as they are offered by, for example, Stem Corporation, Woodrolfe Road, Tollesbury, Essex, CM9 8SE, England or H+P Labortechnik GmbH, Bruckmannring 28, 85764 Oberschleiβheim, Germany, or Firma Radleys, Shirehill, Saffron Walden, Essex, CB-11:3AZ, England may be used for the parallel procedure of the reaction and work-up. For the parallel purification of compounds of the formula (I), or of intermediates obtained during the preparation, use may be made, inter alia, of chromatography apparatuses, for example those from ISCO, Inc., 4700 Superior Street, Lincoln, Nebr. 68504, USA.

The apparatuses mentioned lead to a modular procedure in which the individual process steps are automated, but manual operations have to be performed between the process steps. This can be avoided by employing semi-integrated or fully integrated automation systems where the automation modules in question are operated by, for example, robots. Such automation systems can be obtained, for example, from Zymark Corporation, Zymark Center, Hopkinton, Mass. 01748, USA.

In addition to what has been described here, compounds of the formula (I) may be prepared in part or fully by solid-phase-supported methods. For this purpose, individual intermediate steps or all intermediate steps of the synthesis or of a synthesis adapted to suit the procedure in question are bound to a synthetic resin.

Solid-phase-supported synthesis methods are described extensively in the specialist literature, for example Barry A. Bunin in “The Combinatorial Index”, Verlag Academic Press, 1998.

The use of solid-phase-supported synthesis methods permits a series of protocols which are known from the literature and which, in turn, can be performed manually or in an automated manner. For example, the “tea-bag method” (Houghten, U.S. Pat. No. 4,631,211; Houghten et al., Proc. Natl. Acad. Sci, 1985, 82, 5131-5135), in which products from IRORI, 11149 North Torrey Pines Road, La Jolla, Calif. 92037, USA, are employed, may be semiautomated. The automation of solid-phase-supported parallel syntheses is performed successfully, for example, by apparatuses from Argonaut Technologies, Inc., 887 Industrial Road, San Carlos, Calif. 94070, USA or MultiSynTech GmbH, Wullener Feld 4, 58454 Witten, Germany.

The preparation according to the processes described herein yields compounds of the formula (I) in the form of substance collections which are referred to as libraries. The present invention also relates to libraries which comprise at least two compounds of the formula (I).

The compounds of the formula (I) are suitable for controlling animal pests, in particular insects, arachnids, helminths and mollusks, very especially preferably for controlling insects and arachnids, which are encountered in agriculture, in livestock breeding, in forests, in the protection of stored goods and materials and in the hygiene sector, and have good plant tolerance and favorable toxicity to warm-blooded species. They are active against normally sensitive and resistant species and against all or individual development stages. The abovementioned pests include:

From the order of the Acarina, for example, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Eotetranychus spp., Oligonychus spp. and Eutetranychus spp.

From the order of the Isopoda, for example, Oniscus asselus, Armadium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spp.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea madeira, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Phylloera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. and Damalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralis and Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelus bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylloides chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonumus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrynchus assimilis, Hypera postica, Dermestes spp., Trogoderma, Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conodenus spp., Melolontha melolontha, Amphirmallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hypobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopsis and Ceratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus and Latrodectus mactans.

From the class of helminths, for example, Haemonchus, Trichostrongulus, Ostertagia, Cooperia, Chabertia, Strongyloides, Oesophagostomum, Hyostrongulus, Ancylostoma, Ascaris and Heterakis, as well as Fasciola.

From the class of the Gastropoda, for example, Deroceras spp., Arion spp., Lymnaea spp., Galba spp., Succinea spp., Biomphalaria spp., Bulinus spp. and Oncomelania spp.

From the class of Bivalva, for example, Dreissena spp.

The phytoparasitic nematodes which can be controlled according to the invention include, for example, the root-parasitic soil nematodes, such as, for example, those of the genera Meloidogyne (root gall nematodes, such as Meloidogyne incognita, Meloidogyne hapla and Meloidogyne javanica), Heterodera and Globodera (cyst-forming nematodes, such as Globodera rostochiensis, Globodera pallida and Heterodera trifolii) and of the genera Radopholus, such as Radopholus similis, Pratylenchus, such as Pratylenchus neglectus, Pratylenchus penetrans and Pratylenchus curvitatus;

Tylenchulus, such as Tylenchulus semipenetrans, Tylenchorhynchus, such as Tylenchorhynchus dubius and Tylenchorhynchus claytoni, Rotylenchus, such as Rotylencus robustus, Heliocotylenchus, such as Heliocotylenchus multicinctus, Belonoaimus, such as Belonoaimus longicaudatus, Longidorus, such as Longidorus elongatus, Trichodorus, such as Trichodorus primitivus and Xiphinema, such as Xiphinema index.

The nematode genera Ditylenchus (stem parasites, such as Ditylenchus dipsaci and Ditylenchus destructor), Aphelenchoides (leaf nematodes, such as Aphelenchoides ritzemabosi) and Anguina (blossom nematodes, such as Anguina tritici) can furthermore be controlled with the compounds according to the invention.

The invention also relates to compositions, in particular insecticidal and acaricidal compositions, which comprise one or more compounds of the formula (I) in addition to suitable formulation auxiliaries.

The compositions according to the invention in general comprise from 1 to 95% by weight the active compounds of the formula (I). They can be formulated in various ways, depending on how this is determined by the biological and/or chemico-physical parameters. Suitable formulation possibilities are therefore: Wettable powders (WP), emulsifiable concentrates (EC), aqueous solutions (SL), emulsions, sprayable solutions, oil- or water-based dispersions (SC), suspoemulsions (SE), dusting powders (DP), seed dressings, granules in the form of microgranules, sprayed granules, absorption granules and adsorption granules, water-dispersible granules (WG), ULV formulations, microcapsules, waxes or baits.

These individual types of formulation are known in principle and are described, for example, in: Winnacker-Küchler, “Chemische Technologie” [Chemical Technology], Volume 7, C. Hauser Vedag Munich, 4th Edition 1986; van Falkenberg, “Pesticides Formulations”, Marcel Dekker N.Y., 2nd Edition 1972-73; K. Martens, “Spray Drying Handbook”, 3rd Edition 1979, G. Goodwin Ltd. London.

The necessary formulation auxiliaries, i.e. carrier substances and/or surface-active substances, such as inert materials, surfactants, solvents and further additives, are likewise known and are described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd Edition, Darland Books, Caldwell N.J.; H. v. Olphen, “Introduction to Clay Colloid Chemistry”, 2nd Edition, J. Wiley & Sons, N.Y.; Marsden, “Solvents Guide”, 2nd Edition, Interscience, N.Y. 1950; McCutcheon's, “Detergents and Emulsifiers Annual”, MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, “Encyclopedia of Surface Active Agents”, Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, “Grenzflächenaktive Äthylenoxidaddukte” [Surface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1967; Winnacker-Küchler, “Chemische Technologie” [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th Edition 1986.

Combinations with other substances having a pesticidal action, fertilizers and/or growth regulators can be prepared on the basis of these formulations, for example in the form of a ready-to-use formulation or as a tank mix. Wettable powders are preparations which are uniformly dispersible in water and which, alongside the active compound, and in addition to a diluent or inert substance, also comprise wetting agents, for example polyethoxylated alkylphenols, polyethoxylated fatty alcohols or alkyl- or alkylphenolsulfonates, and dispersing agents, for example sodium ligninsulfonate or sodium 2,2′-dinaphthylmethane-6,6′-disulfonate. Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or also higher-boiling aromatics or hydrocarbons, with the addition of one or more emulsifiers. Emulsifiers which can be used are, for example: calcium alkylarylsulfonates, such as Ca dodecylbenzenesulfonate, or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensation products, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters.

Dusting powders are obtained, for example, by grinding the active compound with finely divided solid substances, for example talc, naturally occurring clays, such as kaolin, bentonite and pyrophillite, or diatomaceous earth. Granules can, for example, be prepared either by spraying the active compound onto granular inert material capable of adsorption or by applying active compound concentrates to the surface of carrier substances, such as sand, kaolinites or granular inert material, by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or mineral oils. Suitable active compounds can also be granulated in the manner customary for the preparation of fertilizer granules—if desired as a mixture with fertilizers.

In wettable powders, the active compound concentration is generally about 10 to 90% by weight, the remainder to make up 100% by weight comprising customary formulation constituents. In emulsifiable concentrates, the active compound concentration can be about 5 to 80% by weight. Dust-like formulations usually comprise 5 to 20% by weight of active compound, and sprayable solutions about 2 to 20% by weight. In granules, the content of active compound partly depends on whether the active compound is present in liquid or solid form and what granulating auxiliaries, fillers and the like are used.

In addition, the active compound formulations mentioned comprise, if appropriate, particular customary tackifiers, wetting agents, dispersing agents, emulsifiers, penetration agents, solvents, fillers or carrier substances.

For use, the concentrates in the commercially available form are diluted in the customary manner, if appropriate, for example by means of water in the case of wettable powders, emulsifiable concentrates, dispersions and in some cases also microgranules. Dust-like and granular formulations as well as sprayable solutions are usually not diluted further with additional inert substances before use.

The required amount applied varies with the external conditions, such as temperature, humidity and the like. It can vary within wide limits, for example between 0.0005 and 10.0 kg/ha or more of active compound, but is preferably between 0.001 and 5 kg/ha.

The active compounds according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations as mixtures with other active compounds, such as other pesticides, for example, insecticides or acaricides, attractants, sterilizing agents, nematicides, fungicides, growth-regulating substances or herbicides. The pesticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, tin compounds and substances produced by microorganisms.

Preferred partners for the mixtures are:

1. from the group of phosphorus compounds

acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, bromophos, bromophos-ethyl, cadusafos (F-67825), chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, demeton, demeton-S-methyl, demeton-S-methyl sulfone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, EPN, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitriothion, fensulfothion, fenthion, fonofos, formothion, fosthiazate (ASC-66824), heptenophos, isazophos, isothioate, isoxathion, malathion, methacrifos, methamidophos, methidathion, salithion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosfolan, phosphocarb (BAS-301), phosmet, phosphamidon, phoxim, pirimiphos, primiphosethyl, pirimiphos-methyl, profenofos, propaphos, proetamphos, prothiofos, pyraclofos, pyridapenthion, quinalphos, suiprofos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thiometon, triazophos, trichlorphon, vamidothion;

2. from the group of carbamates

alanycarb (OK-135), aldicarb, 2-sec-butylphenyl methylcarbamate (BPMC), carbaryl, carbofuran, carbosulfan, cloethocarb, benfuracarb, ethiofencarb, furathiocarb, HCN-801, isoprocarb, methomyl, 5-methyl-m-cumenyl butyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, 1-methylthio(ethylideneamino) N-methyl-N-(morpholinothio)carbamate (UC 51717), triazamate;

3. from the group of carboxylic acid esters

acrinathrin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-(1R)-cis-2,2-di-methyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, beta-cyfluthrin, beta-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentyl isomer), bioresmethrin, bifenthrin, (RS)-1-cyano-1-(6-phenoxy-2-pyridyl)methyl (1RS)-trans-3-(4-tert-butylphenyl)-2,2-dimethylcyclopropanecarboxylate (NCI 85193), cycloprothrin, cyfluthrin, cyhalothrin, cythithrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin (S-41311), lambda-cyhalothrin, permethrin, pheothrin ((R) isomer), prallethrin, pyrethrins (natural products), resmethrin, tefluthrin, tetramethrin, theta-cypermethrin (TD-2344), tralomethrin, transfluthrin and zeta-cypermethrin (F-56701);

4. from the group of amidines

amitraz, chlordimeform;

5. from the group of tin compounds

cyhexatin, fenbutatin oxide;

6. others

abamectin, ABG-9008, acetamiprid, Anagrapha falcitera, AKD-1022, AKD-3059, ANS-118, Bacillus thuringiensis, Beauveria bassianea, bensultap, bifenazate (D-2341), binapacryl, BJL-932, bromopropylate, BTG-504, BTG-505, buprofezin, camphechlor, cartap, chlorobenzilate, chlorfenapyr, chlorfluazuron, 2-(4-chlorophenyl)-4,5-diphenylthiophene (UBI-T 930), chlorfentezine, chromafenozide (ANS-118), CG-216, CG-217, CG-234, A-184699, 2-naphthylmethyl cyclopropanecarboxylate (Ro12-0470), cyromazin, diacloden (thiamethoxam), diafenthiuron, N-(3,5-dichloro-4-(1,1,2,3,3,3-hexafluoro-1-propyloxy)phenyl)carbamoyl)-2-chlorobenzocarboxamide acid ethyl ester, DDT, dicofol, diflubenzuron, N-(2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene)-2,4-xylidine, dinobuton, dinocap, diofenolan, DPX-062, ernamectin-benzoate (MK-244), endosulfan, ethiprole (sulfethiprole), ethofenprox, etoxazole (YI-5301), fenazaquin, fenoxycarb, fipronil, fluazuron, flumite (flufenzine, SZI-121), 2-fluoro-5-(4-(4-ethoxyphenyl)-4-methyl-1-pentyl)diphenyl ether (MTI 800), granulosis and nuclear polyhedrosis viruses, fenpyroximate, fenthiocarb, flubenzimine, flucycloxuron, flufenoxuron, flufenprox (ICI-A5683), fluproxyfen, gamma-HCH, halofenozide (RH-0345), halofenprox (MTI-732), hexaflumuron (DE_(—)473), hexythiazox, HOI-9004, hydramethylnon (AC 217300), lufenuron, imidacloprid, indoxacarb (DPX-MP062), kanemite (AKD-2023), M-020, MTI-446, ivermectin, M-020, methoxyfenozide (Intrepid, RH-2485), milbemectin, NC-196, neemgard, nitenpyram (TI-304), 2-nitromethyl-4,5-dihydro-6H-thiazine (DS 52618), 2-nitromethyl-3,4-dihydrothiazole (SD 35651), 2-nitromethylene-1,2-thiazinan-3-ylcarbamaldehyde (WL 108477), pyriproxyfen (S-71639), NC-196, NC-1111, NNI-9768, novaluron (MCW-275), OK-9701, OK-9601, OK-9602, propargite, pymethrozine, pyridaben, pyrimidifen (SU-8801), RH-0345, RH-2485, RYI-210, S-1283, S-1833, SB7242, SI-8601, silafluofen, silomadine (CG-177), spinosad, SU-9118, tebufenozide, tebufenpyrad (MK-239), teflubenzuron, tetradifon, tetrasul, thiacloprid, thiocyclam, TI-435, tolfenpyrad (OMI-88), triazamate (RH-7988), triflumuron, verbutin, vertalec (Mykotal), YI-5301,

The abovementioned combination partners are known active compounds, and most of them are described in Ch. R. Worthing, S. B. Walker, The Pesticide Manual, 9th Edition (1997), British Crop Protection Council.

The active compound content of the use forms prepared from the commercially available formulations can be from 0.00000001 to 95% by weight of active compound, preferably between 0.00001 and 1% by weight.

The active compounds are used in a customary manner appropriate for the use forms.

The active compounds according to the invention are also suitable for controlling endo- and ectoparasites in the veterinary medicine field and in the field of animal husbandry. The active compounds according to the invention are used here in a known manner, such as by oral use in the form of, for example, tablets, capsules, potions or granules, by means of dermal use in the form of, for example, dipping, spraying, pouring-on, spotting-on and dusting, and by parenteral use in the form of, for example, injection.

The novel compounds of the formula (I) can accordingly also particularly advantageously be used in livestock husbandry (for example cattle, sheep, pigs and poultry, such as chickens, geese and the like). In a preferred embodiment of the invention, the compounds are administered orally to the animals, if appropriate in suitable formulations and if appropriate with the drinking water or feed. Since excretion in the feces takes place in an active manner, the development of insects in the feces of the animals can be prevented very easily in this way. The dosages and formulations suitable in each case depend in particular on the species and the development stage of the stock animals and also on the level of infestation, and can easily be determined and specified by the customary methods. The novel compounds can be employed in cattle, for example, in dosages of 0.01 to 1 mg/kg of body weight.

In addition to the application methods mentioned hereinabove, the active compounds of the formula (I) according to the invention also have excellent systemic action. The active compounds can therefore also be introduced into the plants via below-ground and above-ground parts of plants (root, stem, leaf), when the active compounds are applied in liquid or solid form to the immediate surroundings of the plants (for example granules in soil application, application in flooded rice fields).

Furthermore, the active compounds according to the invention are particularly useful for treating vegetative and generatative propagation stock, such as seed of, for example, cereals, vegetables, cotton, rice, sugar beet and other crops and ornamentals, of bulbs, cuttings and tubers of other vegetatively propagated crops and ornamentals. To this end, treatment can be carried out prior to sowing or planting (for example by special seed dressing techniques, by seed dressings in liquid or solid form or by seed box treatment), during sowing or planting or after sowing or planting by special application techniques (for example seed row treatment). Depending on the application, the amount of active compound applied can vary within a relatively wide range. In general, the application rates are between 1 g and 10 kg of active compound per hectare of soil area.

The compounds of the formula (I) can also be used for controlling harmful plants in crops of known genetically modified plants or of genetically modified plants still to be developed. The transgenic plants generally have particularly advantageous properties, for example resistance to certain crop protection agents, resistance to plant diseases or pathogens of plant diseases, such as certain insects or microorganisms, such as fungi, bacteria or viruses. Other special properties relate, for example, to the harvested product, with respect to quantity, quality, shelf-life, composition and special ingredients. Thus, transgenic plants having increased starch content or a modified quality of the starch or those having a different fatty acid composition of the harvested product are known.

Preference is given to the use in economically important transgenic crops of useful and ornamental plants, for example cereals, such as wheat, barley, rye, oats, millet, rice, manioc and maize, or else crops of sugar beet, cotton, soya, rapeseed, potato, tomato, pea and other vegetable species.

The use in transgenic crops, in particular crops with resistance to insects, is, in addition to the effects with respect to harmful organisms which can be observed in other crops, frequently associated with effects which are specific for the application in the respective transgenic crop, for example a modified or specifically widened spectrum of pests which can be controlled, or modified application rates which can be used for the application.

The invention therefore also provides the use of compounds of the formula (I) for controlling harmful organisms in transgenic crop plants.

The use of the compounds according to the invention comprises, in addition to direct application to the pests, any other application where the compounds of the formula (I) act on the pests. Such indirect applications may be, for example, the use of compounds which decompose or are degraded to compounds of the formula (I), for example in the soil, the plant or the pest.

Herewith, express reference is made to the content of German Patent Application 198 58 192.0, the priority of which is claimed by the present application, and to the summary; it is incorporated into this description by reference:

The examples below serve to illustrate the invention, without implying any limitation.

A. CHEMICAL EXAMPLES Example No. 1 5-Methyl-2-(4-tifluoromethyl-3-pyridyl)-oxazole

N-Propionyl-4-trifluoromethyinicotinamide (6.2 g) and mercury(II) acetate (0.6 g) were heated under reflux in acetic acid (250 ml) for 3 hours. The reaction mixture was subsequently concentrated and the residue was taken up in saturated sodium carbonate solution and extracted with dichloromethane. Chromatographic purification (silica gel, heptane/ethyl acetate) of the crude product gave the desired compound as a colorless oil.

¹H-NMR (CDCl₃, 300 MHz): 2.45 (s, 3H), 6.98 (s, 1H), 7.65 (d, J=5 Hz, 1H), 8.84 (d, J=5 Hz, 1H); 9.32 (s, 1H).

Pure 5-formyl-2-(4-trifluoromethyl-3-pyridyl)-oxazole as a colorless oil was obtained as a byproduct.

¹H-NMR (CDCl₃, 300 MHz): 7.77 (d, J=5 Hz, 1H), 8.05 (s, 1H), 9.00 (d, J=5 Hz, 1H), 9.43 (s, 1H), 9.94 (s, 1H).

Example No. 2 5-n-Propylthiomethyl-2-(4-trifluoromethyl-3-pyridyl)-oxazole

Sodium methoxide (130 μl, 30% in methanol) was added to a solution of 5-bromomethyl-2-(4-trifluoromethyl-3-pyridyl)-oxazole (160 mg) and n-propanethiol (60 μl), in methanol (7 ml), and the mixture was stirred at room temperature for 4 hours. Water (50 ml) was then added, and the mixture was extracted with ethyl acetate. The organic phase was washed with water, dried (MgSO₄), filtered and concentrated. This gave the desired product in pure form as a pale yellow oil.

¹H-NMR (CDCl₃, 300 MHz): 1.02 (t, J=7 Hz, 3H), 1.65 (quin, J=7 Hz, 2H), 2.57 (t, J=7 Hz, 2H), 3.81 (s, 2H), 7.16 (s, 1H), 7.70 (d, J=5 Hz, 1H), 8.88 (d, J=5 Hz, 1H), 9.35 (s, 1H).

The thioethers shown in the tables are prepared in a similar manner.

Example No. 3 5-Cyclopropyl-4-isopropyloxymethyl-2-(4-trifluoromethyl-3-pyridyl)-oxazole

A freshly prepared solution of sodium isopropoxide (20 mg of Na, 5 ml of 2-propanol) was added to a solution of 4-chloromethyl-5-cyclopropyl-2-(4-trifluoromethyl-3-pyridyl)-oxazole (200 mg) in 2-propanol (5 ml), and the mixture was heated under reflux for 10 hours. The reaction mixture was subsequently concentrated, mixed with water and extracted with dichloro-methane. The organic phase was washed with saturated sodium chloride solution, dried (MgSO₄) and filtered through silica gel. Concentration of the organic phase gave the product in pure form as a pale yellow oil.

¹H-NMR (CDCl₃, 300 MHz): 0.99-1.09 (m, 4H), 1.28 (d, J=7 Hz, 2H), 2.05-2.15 (M, 1H), 3.82 (quin, J=7 Hz, 1H), 4.56 (s, 2H), 7.73 (d, J=5 Hz, 1H), 8.80 (d, J=5 Hz, 1H), 9.39 (s, 1H).

The ethers shown in the tables are prepared in a similar manner.

Example No. 4 N-Acetyl, N-methyl-5-aminomethyl-2-(4-trifluoromethyl-3-pyridyl)-oxazole

Acetyl chloride (40 μl) was added to a solution of N-methyl-5-aminomethyl-2-(4-trifluoromethyl-3-pyridyl)-oxazole (150 mg) and triethylamine (90 μl) in dichloromethane (5 ml), and the mixture was stirred at room temperature for one hour. The mixture was then washed with water and saturated sodium bicarbonate, dried (MgSO₄), filtered and concentrated. This gave the pure product as a colorless oil. The ¹H-NMR shows a mixture of rotamers (2:1 ratio).

¹H-NMR (CDCl₃; 300 MHz):

215 and 2.28 (s, 3H), 3.00 and 3.14 (s, 3H), 4.60 and 4.70 (s, 2H), 7.22 (s, 1H), 7.68 and 7.72 (d, J=5 Hz, 1 H), 8.89 and 8.93 (d, J=5H, 1 H), 9.36 (s, 1H).

The amides, carbamates, thiocarbamates, sulfonamides and urea derivatives shown in the tables are prepared in a similar manner.

Example 5 4-Ethoxycarbonyl-5-ethyl-2-(4-trifluoromethyl-3-pyridyloxazole)

A solution of sodium nitrite (4.0 g) in water (6 ml) was added to a solution of ethyl propionoylacetate (7.6 g) in acetic acid (8.0 ml) (temperature from 0 to 10° C.). After one hour at room temperature, 30% strength sulfuric acid (66 ml) and ice-water (80 ml) were added. With efficient cooling and vigorous stirring, zinc powder (62 g) was then added. After 15 minutes, the excess zinc was filtered off and the filtrate was admixed with vigorous stirring with sodium acetate (48.3 g) and freshly prepared 4-trifluoromethyl-pyridine-3-carbonyl chloride (11.5 g). After 2 hours at room temperature, the reaction mixture was extracted with dichloromethane. The organic phase was washed with saturated sodium bicarbonate solution and water, dried (MgSO₄), filtered and concentrated.

Chromatographic purification (silica gel, heptane/ethyl acetate) gave ethyl 2-(4-trifluoromethyl-3-amido)-acetoacetate. This compound (13.2 g), in acetic anhydride (27 ml), was admixed with sulfuric acid (2.3 mol), and the reaction mixture was subsequently stirred at 90° C. for one hour. After cooling, the reaction mixture was concentrated, rendered alkaline using saturated sodium bicarbonate solution, extracted with ethyl acetate, dried (MgSO₄), filtered and concentrated.

This gave the desired product in pure form as colorless crystals (m.p. 76-77° C.).

¹H-NMR (CDCl₃, 300 MHz): 1.33 (t, J=7 Hz, 3H), 1.42 (t, J=7 Hz, 3H), 3.16 (q, J=7 Hz, 2H), 4.45 (q, J=7 Hz, 2H), 7.70 (d, J=5 Hz, 1H), 8.90 (d, J=5 Hz, 1H), 9.38 (s, 1 H).

The 4-ethoxycarbonyl-5-alkyloxazole derivatives shown in the tables are prepared in a similar manner.

Example 6 5-isopropyl-4-dimethylaminocarbonyl-2-(4-trifluoromethyl-3-pyridyl)-oxazole

A suspension of 4-carboxyl-5-isopropyl-2-(4-trifluoromethyl-3-pyridyl)-oxazole (0.8 g) and 1,1′-carbonyldiimidazole (0.5 g) in 1,4-dioxane (70 ml) was stirred at 80° C. for 2 hours. At 50° C., dimethylamine was then introduced for 30 minutes, and the mixture was stirred for another hour. After cooling, water (400 ml) was added and the mixture was extracted with dichloromethane. The organic phase was washed with 5% strength aqueous potassium hydrogen sulfate and water, dried (MgSO₄) and filtered.

Concentration of the organic phase gave the product in pure form as colorless crystals (m.p. 91-92° C.)

¹H-NMR (CDCl₃, 300 MHz): 1.37 (d, J=7 Hz, 6H), 3.12 (s, 3H), 3.35 (s, 3H), 3.70 (quin. J=7 Hz, 1H), 7.70 (d, J=5 Hz, 1H), 8.8, (d, J=5 Hz, 1H), 9.36 (s, 1H).

The oxazole carboxamides shown in the tables are prepared in a similar manner.

TABLE 1

Physical m R¹ properties  1 0 CH₂SOCH₃  2 0 CON(CH₂)₄  3 0 CH₂SCH(CH₂)₅  4 0 CH₂OCH(CH₃)₂ oil  5 0 CH₂OC(O)CH₂CN  6 0 CONH(CH₂)₃CH₃  7 0 CONHCH₂-cyclo-C₃H₅  8 0 CON(CH₃)C₂H₅  9 0 CH₂OC(O)C₂H₅  10 0 CH₂Br crystalline  11 0 CH₂OCH₂CH═CH₂  12 0 CO₂CH₂Ph  13 0

 14 0 CH₂N(CH₃)COCH₃ oil  15 0 CH₂OC(O)CH₂CO₂CH₃  16 0 CH₂NH₂  17 0 CH₂N(CH₃)CO₂CH₂CH═CH₂ oil  18 0 CH₂N(CH₂)₅  19 0 CH₂NHCH(CH₃)₂  20 0 CH₂OCO₂CH₂CH(CH₃)₂  21 0 CH₂OC(O)CH(CH₃)₂  22 0 CH₂N(C₂H₅)COCH₃  23 0 CH₂SOCH₂-2-furfuryl  24 0 CON(CH₃)CH₂CH═CH₂  25 0 CH₂N(CH₃)(CH₂)₂N(CH₃)₂  26 0 CHBr₂ crystalline  27 0 CON(CH₃)CH₂CH₂OC(O)CH₃  28 0 CH₂OC(O)C(CH₃)₃  29 0 CH₂NH(CH₂)₂OCH₃  30 0 CH₂NHCO₂C₂H₅  31 0 CH₂NHC(O)N(CH₃)₂  32 0 CH₂SCH₂CF₃ oil  33 0 CON(CH₃)CH₂-cyclo-C₃H₅  34 1 CH₂SO₂CH₃  35 1 CH₂S(O)₂CH₂CF₃ m.p. 185-187° C.  36 0 CH₂N(CH₃)C(O)N(CH₃)₂  37 0 CH₂SCH₃ oil  38 0 CONHC₂H₅  39 0 CON(CH₃)₂ crystalline  40 0 CH₂O(CH₂)₃CH₃  41 0 CH₂NHCO-cyclo-C₃H₅  42 0 CH₂S(O)CH₂CF₃ m.p. 111-112° C.  43 0 CH₂(O(CH₂)₂)₂OCH₃  44 0 CH₂OCH₂CH(CH₃)₂  45 0 CH₂OCH₂-cyclo-C₃H₅  47 0 CH₂N(C₂H₅)₂ oil  48 0 CH₂NHCH₂CF₃  49 0 CH₂SC₂H₅  50 0 CH₂N(C₂H₅)CH₂CH₂OCH═CH₂  51 1 CH₂SO₂(CH₂)₂OCH₃  52 0 CH₂N(CH₃)SO₂CH₃ oil  53 0 CH₃ oil  54 0 CH₂S(O)₂CH₂CH₂CH₃ crystalline  55 0 CH(OCH(CH₃)₂)₂  56 0 CH₂NHCH₃ oil  57 0

 58 0 CH₂NHCO(CH₂)₂SCH₃  59 0 CON(CH₃)CH(OCH₃)₂  60 0 CONHCH₃  61 0 CH₂N(CH₃)C(CH₃)₃  62 0 CON(CH₃)-n-C₃H₇  63 0 CH₂NHCOCH₃  64 0 CONHCH₂CH═CH₂  65 0 CONH(CH₂)₂OCH₃  66 0 CH₂NHCO-cyclo-C₄H₇  67 0 CH₂NHC₂H₅  68 0 CH₂SO₂CH₂-2-furfuryl  69 0 CH₂SO₂(CH₂)₂OCH₃  70 0 CH₂N(CH₃)COCH₂OCH₃ oil  71 0

 72 0 CH₂NHCOCH═C(H)CH₃  73 0 CH₂N(CH₃)CO₂CH₂CH(CH₃)₂  74 0 CH₂SCH₂CH═CH₂  75 0 CH₂OC(O)CH₂CH₂CH₃  76 0 CONHC₃H₇  77 0 CH₂N(CH₃)CH₂CN  78 0 CH₂OCH₃ oil  79 0

 80 0 CON(CH₂)₅  81 0 CH₂S(O)CH₂CH₂CH₃ oil  82 0 CH₂N(CH₃)CO₂C₂H₅ oil  83 0 CH₂N(CH₃)-cyclo-C₆H₁₁  84 0 CH₂N(CH₃)COC₂H₅ oil  85 0 CH₂NHCOCH(CH₃)₂  86 0 CH₂SC(CH₃)₃  87 0 CH₂S(CH₂)₃OH  88 0

 89 0 CONHCH₂C≡CH  90 0 CH₂N(C₂H₅)CH₂CH═CH₂  91 0 CH₂N(C₂H₅)C(O)(CH₂)₂CH═CH₂  92 0 CH₂N(CH₃)COCO₂CH₃ oil  93 0 CH₂N(CH₃)SO₂CH₂CF₃ oil  94 0 CH₂SCH₂CH(CH₃)₂ oil  95 0 CH₂N(CH₃)CH₂CO₂CH₃  96 0 CO₂C(CH₃)₃  97 0 CON(CH₃)-n-C₄H₉  98 0 CON(CH₃)CH₂CH₂N(CH₃)₂  99 0 CH₂O(CH₂)₂CH₃ 100 0

oil 101 0 CH₂SO(CH₂)₂OCH₃ 102 0 CON(CH₃)C₂H₅ crystalline 103 0 CH₂NHCOCH₂CH(CH₃)₂ 104 0 CH₂NHSO₂C₂H₅ 105 0 105 0

106 0

107 0 CON(CH₃)CH₂CN 108 0 CH₂Cl 110 0 CH₂OCH₂CF₃ 111 0 CH₂N(CH₃)SO₂C₂H₅ oil 112 0

113 0 CH₂NHCO₂CH₂CH═CH₂ 114 0 CH₂N(CH₃)COCH₂-cyclo-C₅H₉ 115 0 CH₂SCH(CH₂)₄ 116 0

crystaliine 117 0 CH₂NHCOCH₂SCH₃ 118 0 CH₂S(O)₂CH₂CF₃ m.p. 119-120° C. 119 0 CH₂NH(CH₂)₃CH₃ oil 120 0 CH(OC₂H₅)₂ 121 0 CH₂CO₂C(CH₃)₃ 122 0 CH₂CN 123 0 CH₂SCH₂-2-pyrimidyl 124 0 CH₂NHC(O)S(CH₂)₂CH₃ 125 0 CH₂N(CH₃)CO-cyclo-C₃H₅ oil 126 1 CH₂SO₂CH₂-2-furfuryl 127 0 CH₂N(CH₃)COCH₂SCH₃ 128 0 CH₂NHSO₂CH(CH₃)₂ 129 0 CON(CH₃)(CH₂)₂CH(CH₃)₂ 130 0 CH₂NHCO₂CH₂CH(CH₃)₂ 131 0 CO₂-cyclo-C₃H₅ 132 0 CH₂OCH₂C≡CH 133 0 CH₂OC(O)CO₂CH₃ 134 0 CH₂OC(O)CH₂CH₂Si(CH₃)₃ 135 0 CO₂H m.p. 212-214° C. 136 0 CH₂SCH₂CH₂CH₃ oil 137 0 CH₂N(CH₃)CO(CH₂)₂SCH₃ 138 0 CH₂CO₂CH₂Ph 139 0 CO₂CH₃ 140 0 CH₂SCH₂CH₂OH 141 0 CH₂NHCH₂C≡CH 142 0 CH₂O(CH₂)₂OCH₃ 143 0 CH₂OC(O)N(CH₃)₂ 144 0 CH₂F 145 0

146 0 CH₂NHC(O)SCH₃ 147 0 CH₂N(CH₃)C(O)SCH₃ oil 148 0 CH₂NHCO₂CH₂CH₂Cl 149 0 CH₂CO₂-cyclo-C₃H₅ 150 0 CH₂NHCO(CH₂)₂CH═CH₂ 151 0 CH₂N(CH₃)CO-cyclo-C₄H₇ 152 0 CH₂SO₂CH₃ 153 0

154 0 CH₂S(CH₂)₂N(CH₃)₂ 155 0 CON(CH₃)CH₂CH₂CN 156 0 CH₂NHC(O)SPh 157 0 157 0

158 0 CONHCH₂CN 159 0 CH(OCH₃)₂ 160 0 CH₂SCH₂-2-furfuryl 161 0 CH₂N(CH₃)CH(CH₃)₂ 162 0 CH₂OCO₂CH₃ 164 0 CHO oil 165 0

166 0

167 0 CON(CH₂)₃ 168 1 CH₂S(O)₂CH₂CH₂CH₃ m.p. 136-137° C. 169 0

170 0 CH₂OC(O)CH₂CH(CH₃)₂ 171 0 CONHCH(CH₃)₂ 172 0 CH₂NHSO₂CH₂CF₃ 173 0 CH₂NHCOCH₂-cyclo-C₅H₉ 174 0 CH₂OH oil 175 0 CON(CH₃)OCH₃ 176 0 CONHC(CH₃)₃ 177 0 CH₂NH-cyclo-C₃H₅ 178 0 CONHCH₂CF₃ 180 0 CH₂OC(O)CH═CH₂ 181 0 CH₂SCH₂-cyclo-C₃H₅ 182 0 CH₂SCH₂CH₂OCH₃ 183 0 CH₂SCH₂-2-pyridyl 184 0

185 0 CH₂N(CH₃)CO₂CH₂CH₂Cl 186 0 CH₂OC(O)CH₃ 187 0 CH₂N(CH₃)COCH(CH₃)₂ oil

TABLE 2

Physical m R² properties  1 0 CH₂CO₂CH₃  2 0 CH₂N(CH₃)CH(CH₃)₂  3 0 CH₂NHCOCH₂SCH₃  4 0 CH₂SCH₂CH₂OH  5 0 CH₂N(C₂H₅)CH₂CH₂OCH═CH₂  6 0 CH₂OC(O)CH₃  7 0 CH₂OC(O)CH₂CH₂Si(CH₃)₃  8 0 CH₂S(CH₂)₃OH  9 1 CH₂SO₂CH₂-2-furfuryl  10 0 CH₂SO₂CH₂CF₃  11 0 CH₂OCH₂CH(CH₃)₂  12 0

 13 0 CH₂N(CH₃)COcycloC₃H₅  14 0 CONH(CH₂)₂OCH₃ m.p. 91-92° C.  15 0 CH₂OC₂H₅  16 0 CH₂N(C₂H₅)₂  17 0 CONH(CH₂)₃CH₃ m.p. 69-70° C.  18 0 CON(CH₂)₄  19 0 CH₂SCH₂-2-furfuryl  20 0 CH₂NHCO₂CH₂CH₂Cl  21 0 CON(CH₃)CH₂CH₂OC(O)CH₃  22 0 CH₂CO₂CH₂Ph  23 0

 24 0 CON(CH₃)CH₂CH═CH₂ crystalline  25 0 CH₂NHSO₂CH(CH₃)₂  26 0 CH₂SCH₂-2-pyridyl  27 0 CH₂OC(O)CH₂CO₂CH₃  28 0 CH₂Br  29 0 CONHC(CH₃)₃  30 0 CH₂NHCH₃  31 0 CH₂NH(CH₂)₃CH₃  32 0 CH₂NHC(O)N(CH₃)₂  33 0 CON(CH₃)OCH₃  34 0 CH₂SCH(CH₂)₅  35 0 CH₂N(CH₃)CO₂C₂H₅  36 0 CONHCH₂-cyclo-C₃H₅ crystalline  37 0 CH₂NHCO-cyclo-C₃H₅  38 0 CH₂NHCO₂CH₂CH═CH₂  39 0 CH₂OC(O)C(CH₃)₃  40 0 CH₂O(CH₂)₃CH₃  41 0 CH₂NHC(O)S(CH₂)₂CH₃  42 0 CH₂NHCO-cyclo-C₄H₇  43 0 CH₂F  44 0 CH₂OCH₂C≡CH  45 0 CH₂(O(CH₂)₂)₂OCH₃  46 0 CH₂O(CH₂)₂OCH₃  47 0 CH₂SO₂CH₃  48 1 CH₂SO₂CH₃  49 0 CH₂NHCH(CH₃)₂  50 0 CH₂OC(O)CH(CH₃)₂  51 0 CO₂CH₃ m.p. 113-114° C.  52 0 CH₂SCH₂CH₂OCH₃  53 0 CH₂N(CH₃)SO₂CH₂CF₃  54 0 CH₂SOCH₂-2-furfuryl  55 0 CH₂NHCO(CH₂)₂SCH₃  56 0 CON(CH₃)CH(OCH₃)₂  57 0 CH₂SCH₂CH(CH₃)₂  58 0 CO₂C(CH₃)₃  59 0 CH₂N(CH₃)COCH₂SCH₃  60 0 CH₂NHC₂H₅  61 1 CH₂SO₂CH₂CF₃  62 0 CON(CH₃)(CH₂)₂CH(CH₃)₂  63 0 CH₂N(CH₃)C(CH₃)₃  64 0 CH₂N(C₂H₅)C(O)(CH₂)₂CH═CH₂  65 0 CH₂OC(O)CH₂CH₂CH₃  66 0

 67 0 CH₂SC(CH₃)₃  68 0 CH₂N(CH₃)C(O)SCH₃  69 0

 70 0 CONHC₂H₅  71 0 CONHCH₂CN  72 0 CH₂SCH₃ oil  73 0 CH₂CO₂-cyclo-C₃H₅  74 0

 75 0 CH₂SO₂(CH₂)₂OCH₃  76 0 CO₂-cyclo-C₃H₅  77 0 CH₂NHSO₂C₂H₅  78 0 CH₂N(C₂H₅)CH₂CH═CH₂  79 0 CH₂SOCH₂CF₃  80 0 CH₂N(CH₃)-cycloC₆H₁₁  81 0 CH₂N(CH₃)CH₂CO₂CH₃  82 0 CH₂NHCH₂C≡CH  83 0 CH₂S(CH₂)₂N(CH₃)₂  84 0 CONH_(n)-C₃H₇ m.p. 86-87° C.  85 0 CH₂SCH₂-2-pyrimidyl  86 0 CH₂NHC(O)SPh  87 0 CH₂N(CH₃)CO₂CH₂CH═CH₂  88 0 CH₂SOCH₃  89 0 CH₂NH-cyclo-C₃H₅  90 1 CH₂SO₂(CH₂)₂CH₃  91 0 CH₂N(CH₃)COC₂H₅  92 0 CONHCH₂CH═CH₂ m.p. 77-78° C.  93 0 CH₂NH(CH₂)₂OCH₃  94 0 CH₂SCH(CH₂)₄  95 0 CH₂NHCOCH₃  96 1 CH₂SO₂(CH₂)₂OCH₃  97 0 CH₂SO(CH₂)₂CH₃  98 0 CH₂SCH₂CH═CH₂  99 0

100 0 CH₂OC(O)C₂H₅ 101 0 CONHCH(CH₃)₂ oil 102 0 CON(CH₂)₅ 103 0 CH₂N(CH₃)CO(CH₂)₂SCH₃ 104 0 CH₂NHCOCH₂CH(CH₃)₂ 105 0 CH₂N(CH₃)(CH₂)₂N(CH₃)₂ 106 0 CH₂SO(CH₂)₂OCH₃ 107 0 CON(CH₃)C₂H₅ 108 0 CONHCH₂C≡CH m.p. 161-162° C. 109 0 CH₂SCH₂-cyclo-C₃H₅ 110 0 CH₂OCH₂CH═CH₂ 111 0 CH₂N(CH₃)SO₂C₂H₅ 112 0 CH₂NHC(O)SCH₃ 113 0 CH₂S(CH₂)₂CH₃ 114 0 CON(CH₂)₃ 115 0 CH₂N(CH₃)CO-cyclo-C₄H₇ 116 0 CH₂OCO₂CH₂CH(CH₃)₂ 117 0 CH₂CO₂C(CH₃)₃ 118 0 CON(CH₃)CH₂CH₂CN 120 0 CH₂OC(O)CO₂CH₃ 121 0 CON(CH₃)CH₂CN 122 0 CH₂O(CH₂)₂CH₃ 123 0 CH₂N(CH₃)CO₂CH₂CH₂Cl 124 0 CH₂NHCH₂CF₃ 125 0 CONHCH₃ 126 0 CH₂OCO₂CH₃ 127 0 CH₂SCH₃CF₃ 128 0 CH₂NH₂ 129 0 CON(CH₃)-n-C₃H₇ 130 0 CH₂N(CH₃)COCH₂-cyclo-C₅H₉ 131 0

132 0 CH₂NHSO₂CH₂CF₃ 133 0 CON(CH₃)-n-C₄H₉ crystalline 134 0 CH₂I 135 0 CH₂N(CH₃)CO₂CH₂CH(CH₃)₂ 136 0 CH₂OC(O)CH₂CH(CH₃)₂ 137 0 CH₂SO₂(CH₂)₂CH3 138 0

139 0 CH₂OC(O)N(CH₃)₂ 140 0 CH₂N(CH₃)COCH₃ 141 0 CH₂SO₂CH₂-2-furfuryl 142 0 CH₂OCH₂CF₃ 143 0 CH₂NHCO₂C₂H₅ 144 0 CH₂N(CH₃)C(O)N(CH₃)₂ 145 0 CH₂OC(O)CH═CH₂ 146 0 CON(CH₃)CH₂-cyclo-C₃H₅ 147 0 CH₂N(CH₃)COCH₂OCH₃ 148 0 CH₂SC₂H₅ 149 0 CH₂N(CH₂)₅ 150 0 CO₂CH₂Ph 151 0 CH₂NHCOCH═CH)CH₃ 152 0 CH₂NHCOCH₂-cyclo-C₅H₉ 153 0 CH₂Cl wax 154 0 CH₂CN 155 0 CONHCH₂CF₃ 156 0 CH₂N(C₂H₅)COCH₃ 157 0 CH₂N(CH₃)SO₂CH₃ 158 0 CH₂N(CH₃)CH₂CN 159 0 CON(CH₃)CH₂CH₂N(CH₃)₂ 160 0 CH₂N(CH₃)COCH(CH₃)₂ 161 0 CH₂NHCOCH(CH₃)₂ 162 0

m.p. 126-127° C. 163 0 CH₂N(CH₃)₂ 164 0 CH₂OC(O)CH₂CN 165 0 CH₂OCH₂-cyclo-C₃H₅ 166 0 CH₂NHCO(CH₂)₂CH)═CH₂ 167 0

168 0 CH₂NHCO₂CH₂CH(CH₃)₂ 169 0 CO₂Et oil 170 0 CH₂OCH₃ oil 171 0

m.p. 65-66° C. 172 0

oil 173 0 CONH(CH₂)₃OCH₃ oil 174 0 CH₂OH m.p. 64-65° C. 175 0 CO₂H m.p. 213-214° C. 176 0 CH₂CH₃ oil

TABLE 3a

Physical m R² properties  1 0 CH₂N(CH₃)(CH₂)₂N(CH₃)₂  2 0 CH₂N(CH₃)SO₂CH₃  3 0 CH₂SO₂(CH₂)₂OCH₃  4 0

 5 0 CH₂NHCH₃ oil  6 0 CH₂NHCO₂CH₂CH═CH₂  7 0 CH₂NHCOCH═C(H)CH₃  8 0 CH₂SO₂CH₂-2-furfuryl  9 0 CH₂NHCH₂C≡CH  10 0

 11 0 CONHCH₂C≡CH m.p. 105-107° C.  12 0 CH₂SOCH₂CF₃  13 0 CH₂SC(CH₃)₃  14 0 CH₂OCH₂C≡CH  15 0 CH₂SOCH₂-2-furfuryl  17 0 CH₂OCH₂-cyclo-C₃H₅  18 0 CON(CH₃)-n-C₃H₇ oil  19 0 CH₂OC(O)CH₃  20 0 CH₂NHSO₂C₂H₅  21 0 CON(CH₃)-n-C₄H₉ oil  22 0 CH₂N(CH₃)-cyclo-C₆H₁₁  23 0 CH₂OC(O)C₂H₅  24 0 CON(CH₃)CH(OCH₃)₂  25 0 CH₂NHC(O)S(CH₂)₂CH₃  26 0 CH₂SO₂CH₃  27 0 CH₂NHCOCH(CH₃)₂  28 0 CH₂N(CH₃)COCH₂SCH₃  29 0 CH₂CO₂-cyclo-C₃H₅  30 0 CH₂N(CH₃)CO-cyclo-C₄H₇  31 0 CH₂OC(O)N(CH₃)₂  32 0

 33 0 CH₂NH(CH₂)₃CH₃  34 0 CO₂C(CH₃)₃  35 0 CH₂SCH₂CH(CH₃)₂  36 1 CH₂SO₂(CH₂)₂CH₃  37 0 CH₂CO₂H m.p. 140-141° C.  38 0 CH₂NHCO(CH₂)₂CH═CH₂  39 0

 40 0 CONH-n-C₃H₇ m.p. 47-49° C.  41 0 CH₂N(C₂H₅)₂  42 0 CH₂N(CH₃)CO₂CH₂CH₂Cl  43 0 CONHCH₃  44 0 CONHCH(CH₃)₂  45 0 CONH(CH₂)₂OCH₃ m.p. 62-63° C.  46 0 CH₂SCH₂-2-furfuryl  47 0 CONHCH₂CN  48 0 CH₂S(CH₂)₂N(CH₃)₂  49 0 CH₂OC(O)CH═CH₂  50 0 CH₂NHCO(CH₂)₂SCH₃  51 0 CH₂OCH₂CH═CH₂  52 0 CH₂CO₂CH₃  53 0 CH₂N(CH₃)COCH₃ oil  54 0 CO₂CH₃  55 0 CH₂SO(CH₂)₂OCH₃  56 0 CON(CH₃)CH₂CH═CH₂ oil  57 1 CH₂SO₂CH₂-2-furfuryl  58 0 CH₂NH(CH₂)₂OCH₃  59 0 CH₂SCH₂CH═CH₂  60 0 CH₂I  61 0 CH₂SCH₂-2-pyrimidyl  62 0 CON(CH₃)CH₂CH₂N(CH₃)₂  63 0 CH₂N(CH₃)SO₂CH₂CF₃ oil  64 0 CH₂O(CH₂)₃CH₃  65 0 CH₂NHCOCH₂-cyclo-C₅H₉  66 0 CH₂SO(CH₂)₂CH₃  67 0 CO₂CH₂Ph  68 0 CH₂Br  69 0 CH₂OC(O)CH(CH₃)₂  70 0 CH₂OC(O)CH₂CH(CH₃)₂  71 0 CH₂OCH₂CF₃  72 0 CH₂N(CH₃)CO-cyclo-C₃H₅  73 0 CH₂N(CH₃)CH₂CO₂CH₃  74 0 CON(CH₃)₂  75 0 CON(CH₂)₄  76 0 CH₂O(CH₂)₂OCH₃  77 0 CH₂NHC(O)SPh  78 0 CH₂NHCO₂C₂H₅  79 0

 80 0 CH₂N(CH₃)SO₂C₂H₅  81 0 CH₂NHSO₂CH(CH₃)₂  82 0 CH₂OC(O)CH₂CH₂Si(CH₃)₃  83 0 CO₂-cyclo-C₃H₅  84 0 CH₂OCH(CH₂)₃ oil  85 0 CH₂SOCH₃  86 0

 87 0 CH₂S(CH₂)₂CH₃  88 0 CH₂SCH₂-2-pyridyl  89 0 CH₂OC(O)CH₂CN  90 0

 91 0 CH₂N(CH₃)COCH₃ oil  92 0 CH₂CN  93 0 CH₂OC(O)CO₂CH₃  94 1 CH₂SO₂CH₃  95 0 CH₂CON(CH₃)₂ m.p. 85-86° C.  96 0 CH₂CO₂CH₂Ph  97 0 CH₂SO₂(CH₂)₂CH3  98 0 CH₂N(CH₃)C(O)N(CH₃)₂  99 0 CONHCH₂-cyclo-C₃H₅ m.p. 79-81° C. 100 0 CH₂OCH₂CH(CH₃)₂ 101 0 CH₂SCH(CH₂)₄ 102 0 CON(CH₃)OCH₃ 103 0 CH₂N(CH₃)COCH(CH₃)₂ 104 0 CH₂N(CH₃)CO₂CH₂CH(CH₃)₂ 105 0 CH₂N(C₂H₅)COCH₃ 107 0 CH₂NHCH₂CF₃ 108 0 CH₂N(CH₃)COCH₂-cyclo-C₅H₉ 109 0 CH₂N(CH₃)C(O)SCH₃ 110 0 CONH(CH₂)₃CH₃ wax 111 0 CH₂NHCO₂CH₂CH₂Cl 112 0 CH₂OCO₂CH₃ 113 0 CH₂NH₂ 114 0 CON(CH₃)C₂H₅ 115 0 CH₂SCH₂CH₂OCH₃ 116 0 CH₂N(CH₃)CH₂CN 117 0 CH₂N(CH₃)CH(CH₃)₂ 118 0 CON(CH₃)CH₂-cyclo-C₃H₅ 119 0 CH₂N(CH₃)COCH₂OCH₃ 120 0 CH₂NHCOCH₂CH(CH₃)₂ 121 0 CON(CH₃)CH₂CN 122 0 CH₂OCH₂CF₃ 123 0 CH₂SC₂H₅ 124 0 CH₂OC(O)CH₂CO₂CH₃ 125 0 CH₂N(CH₃)SO₂CH₂CF₃ oil 126 0 CH₂N(C₂H₅)CH₂CH═CH₂ 127 0 CH₂N(CH₃)C(CH₃)₃ 128 0 CH₂(O(CH₂)₂)₂OCH₃ 129 0 CON(CH₂)₅ 130 0 CH₂SCH₂CH₂OH 131 0 CH₂NHSO₂CH₂CF₃ 132 0 CH₂N(CH₃)CO₂CH₂CH═CH₂ 133 0 CON(CH₃)CH₂CH₂OC(O)CH₃ 134 0 CH₂N(CH₃)CO(CH₂)₂SCH₃ 135 0 CH₂F 136 0 CH₂NHCOCH₂SCH₃ 137 0 CH₂OCO₂CH₂CH(CH₃)₂ 138 1 CH₂SO₂CH₂CF₃ 139 0 CH₂OH crystalline 140 0 CH₂NHCH(CH₃)₂ 141 0

142 0 CONHCH₂CH═CH₂ crystalline 143 0

144 0 CH₂O(CH₂)₂CH₃ 145 0 CH₂NHCO-cyclo-C₄H₇ 146 0 CH₂OC₂H₅ oil 147 0 CH₂NHC₂H₅ 148 0 CH₂N(C₂H₅)CH₂CH₂OCH═CH₂ 149 0 CH₂SCH(CH₂)₅ 150 0 CONHC₂H₅ 151 0 CH₂OC(O)CH₂CH₂CH₃ 152 0 CH₂NH-cyclo-C₃H₅ 153 0 CH₂NHC(O)N(CH₃)₂ 154 0 CH₂NHC(O)SCH₃ 155 0 CON(CH₃)(CH₂)₂CH(CH₃)₂ 156 0

157 0 CH₂NHCO₂CH₂CH(CH₃)₂ 158 0 CH₂SO₂CH₂CF₃ 159 0 CH₂NHCOCH₃ 160 0 CH₂S(CH₂)₃OH 161 0 CH₂CO₂C₂H₅ oil 162 0 CH₂N(CH₃)CO₂C₂H₅ 163 0 CONHCH₂CF₃ 164 0 CH₂OCH₃ oil 165 0 CH₂CO₂C(CH₃)₃ 166 0 CH₂Cl oil 167 0 CH₂N(CH₂)₅ 168 0 CH₂NHCO-cyclo-C₃H₅ 169 0 CONHC(CH₃)₃ 170 1 CH₂SO₂(CH₂)₂OCH₃ 171 0 CON(CH₃)CH₂CH₂CN 172 0 CH₂OC(O)C(CH₃)₃ 173 0 CH₂SCH₂-cyclo-C₃H₅ 174 0 CH₂N(CH₃)COC₂H₅ 175 0 CH₂N(C₂H₅)C(O)(CH₂)₂CH═CH₂ 176 0 CONH(CH₂)₃CH₃ oil 177 0 CONH(CH₂)₃OCH₃ oil 178 0 CON(CH₃)CH₂CH(OCH₃)₂ oil 179 0 CONHCH₂C(CH₃)₃ m.p. 123-125° C. 180 0 CON(CH₃)CH₂C≡CH wax 181 0 CON(CH₃)CH(CH₃)₂ m.p. 80-81° C. 182 0 CONHCH₂CH(OCH₃)₂ m.p. 75-76° C. 183 0 CONH-cyclohexyl m.p. 120-121° C. 184 0 CON(CH₃)-cyclohexyl m.p. 94-95° C.

TABLE 3b

Physical m R² properties 176a 0 CH₂CN 177a 0 CH₂S(CH₂)₂CH₃ 178a 0 CH₂OC(O)CO₂CH₃ 179a 0 CON(CH₃)(CH₂)₂CH(CH₃)₂ 180a 0 CH₂N(CH₃)CO₂C₂H₅ 181a 1 CH₂SO₂CH₃ 182a 0 CH₂CO₂CH₂Ph 183a 0 CH₂NH(CH₂)₂OCH₃ 184a 0 CH₂N(CH₃)C(O)N(CH₃)₂ 185 0 CH₂SCH(CH₂)₄ 186 0 CON(CH₃)C₂H₅ 187 0 CH₂N(CH₃)COCH₂OCH₃ 188 0 CH₂OCH₂CF₃ 189 0 CH₂N(CH₃)SO₂CH₂CF₃ 190 0 CH₂N(CH₃)CO(CH₂)₂SCH₃ 191 0 CH₂NHC(O)SCH₃ 192 0 CH₂SO₂CH₂CF₃ 193 0 CH₂S(CH₂)₃OH 194 0 CH₂SO₂(CH₂)₂OCH₃ 195 0 CH₂N(CH₃)CH₂CN 196 0 CH₂N(C₂H₅)CH₂CH═CH₂ 197 0 CH₂N(CH₃)C(CH₃)₃ 198 1 CH₂SO₂CH₂CF₃ 199 0 CH₂N(CH₂)₅ 200 0 CH₂N(CH₃)COCH(CH₃)₂ 201 0 CH₂NHCH₂CF₃ 202 0 CH₂F 203 0 CONHCH₂CH═CH₂ 204 0 CH₂OCH₃ 205 0 CH₂NHCOCH₂SCH₃ 206 0

207 0 CH₂CO₂H 208 0 CH₂OCO₂CH₃ 209 0 CH₂N(CH₃)SO₂CH₃ 210 0 CH₂NHCOCH═C(H)CH₃ 211 0 CH₂SCH(CH₂)₅ 212 0

213 0 CONHC(CH₃)₃ 214 0 CH₂N(C₂H₅)CH₂CH₂OCH═CH₂ 215 0 CH₂OCH(CH₂)₃ 216 0 CH₂N(CH₃)(CH₂)₂N(CH₃)₂ 217 0 CH₂N(CH₃)CO-cyclo-C₄H₇ 218 0 CH₂OC(O)CH₂CN 219 0 CH₂N(CH₃)COCH₂SCH₃ 220 0 CO₂-cyclo-C₃H₅ 221 0 CH₂N(CH₃)-cyclo-C₆H₁₁ 222 0 CH₂NHSO₂CH₂CF₃ 223 0 CON(CH₃)CH₂CH₂OC(O)CH₃ 224 0 CH₂OC(O)CH₂CH₂CH₃ 225 0 CH₂NHC(O)N(CH₃)₂ 226 0 CH₂SCH₂-cyclo-C₃H₅ 227 0 CON(CH₃)₂ 228 0 CON(CH₃)-n-C₃H₇ 229 0

230 0 CONHCH₂CN 231 0 CONH(CH₂)₂OCH₃ 232 0 CH₂OC(O)CH(CH₃)₂ 233 0 CH₂I 234 0 CH₂N(C₂H₅)₂ 235 0 CH₂CO₂CH₃ 236 0 CONHCH₃ 237 0 CH₂NHCO(CH₂)₂CH═CH₂ 238 0 CH₂SCH₂CH(CH₃)₂ 239 0 CO₂C(CH₃)₃ 240 0 CH₂NHCO₂C₂H₅ 241 0 CH₂OCH₂C≡CH 242 0 CH₂OC(O)CH₂CH(CH₃)₂ 243 0 CH₂SCH₂CH₂OH 244 0 CON(CH₃)CH₂CH═CH₂ 245 0 CH₂SCH₂-2-furfuryl 246 0 CH₂O(CH₂)₂CH₃ 247 0 CH₂CO₂-cyclo-C₃H₅ 248 0 CON(CH₂)₅ 249 0 CH₂NHCH(CH₃)₂ 250 0 CH₂S(CH₂)₂N(CH₃)₂ 251 0 CON(CH₃)CH(OCH₃)₂ 252 0 CH₂SOCH₃ 253 0 CONHCH(CH₃)₂ 254 0 CH₂OC(O)CH₂CH₂Si(CH₃)₃ 255 0 CH₂SCH₂-2-pyrimidyl 256 0 CH₂SOCH₂-2-furfuryl 257 0 CON(CH₃)-n-C₄H₉ 258 0 CH₂OC(O)CH═CH₂ 259 0

260 0 CH₂SCH₂-2-pyridyl 261 0

262 0 CON(CH₃)CH₂CH₂N(CH₃)₂ 263 0 CH₂N(CH₃)C(O)SCH₃ 264 0 CH₂SO₂CH₂-2-furfuryl 265 0 CH₂OCH₂-cyclo-C₃H₅ 266 0 CONH(CH₂)₃CH₃ 267 0 CH₂OC₂H₅ crystalline 268 0 CH₂NHC(O)SPh 269 0 CH₂(O(CH₂)₂)₂OCH₃ 270 0 CH₂SC(CH₃)₃ 271 0 CH₂O(CH₂)₂OCH₃ 272 1 CH₂SO₂CH₂-2-furfuryl 273 0 CH₂CON(CH₃)₂ m.p. 113-114° C. 274 0

275 0 CH₂OC(O)C(CH₃)₃ 276 0 CH₂Br 277 0 CH₂SO₂(CH₂)₂CH₃ 278 0 CONHCH₂-cyclo-C₃H₅ 279 0 CH₂SOCH₂CF₃ 280 0 CH₂OCH₂CH(CH₃)₂ 281 0 CH₂OC(O)N(CH₃)₂ 282 0 CON(CH₃)OCH₃ 283 0 CH₂N(CH₃)CO₂CH₂CH(CH₃)₂ 284 0

285 0 CH₂N(C₂H₅)COCH₃ 286 0 CONHCH₂C≡CH 287 0 CH₂N(CH₃)COCH₂-cyclo-C₅H₉ 288 1 CH₂SO₂(CH₂)₂CH₃ 289 0 CH₂NHCO₂CH₂CH₂Cl 290 0 CH₂N(CH₃)CO-cyclo-C₃H₅ 291 0 CH₂NH₂ 292 0

293 0 CH₂SCH₂CH₂OCH₃ 294 0 CH₂N(CH₃)CH(CH₃)₂ 295 0 CH₂SO₂CH₃ 296 0 CON(CH₃)CH₂-cyclo-C₃H₅ 297 0 CH₂NHCOCH₂CH(CH₃)₂ 298 0 CH₂NHC(O)S(CH₂)₂CH₃ 299 0 CON(CH₃)CH₂CN 300 0 CH₂SC₂H₅ 301 0 CON(CH₂)₄ 302 0 CH₂OC(O)CH₂CO₂CH₃ 304 0 CH₂SO(CH₂)₂OCH₃ 305 0 CH₂N(CH₃)COC₂H₅ 306 0 CH₂NHSO₂C₂H₅ 307 0 CH₂OC(O)CH₃ 308 0 CO₂CH₂Ph 309 0 CH₂N(CH₃)CO₂CH₂CH═CH₂ 310 0 CH₂OC(O)C₂H₅ 311 0 CH₂OCH₂CF₃ 312 0 CH₂OCO₂CH₂CH(CH₃)₂ 313 0 CH₂SO(CH₂)₂CH₃ 314 0 CH₂OH m.p. 159‥160° C. 315 0 CO₂CH₃ 316 0

317 0 CH₂NHCH₂C≡CH 318 0 CH₂N(CH₃)CH₂CO₂CH₃ 319 0 CH₂NHCO-cyclo-C₄H₇ 320 0 CH₂N(CH₃)SO₂CH₂CF₃ 321 0 CH₂NHC₂H₅ 322 0 CH₂N(CH₃)COCH₃ 323 0 CONHC₂H₅ 324 0 CH₂NHCH₃ 325 0 CH₂NH-cyclo-C₃H₅ 326 0 CH₂N(CH₃)CO₂CH₂CH₂Cl 327 0 CH₂NHSO₂CH(CH₃)₂ 328 0

329 0 CH₂NHCO(CH₂)₂SCH₃ 330 0 CH₂NHCOCH(CH₃)₂ 331 0 CH₂NHCOCH₃ 332 0 CH₂NHCOCH₂-cyclo-C₅H₉ 333 0 CH₂SCH₂CH═CH₂ 334 0 CH₂CO₂C₂H₅ 335 0 CH₂NH(CH₂)₃CH₃ 336 0 CONHCH₂CF₃ 337 0 CH₂O(CH₂)₃CH₃ 338 0 CH₂CO₂C(CH₃)₃ 339 0 CH₂Cl 340 0 CH₂NHCO-cyclo-C₃H₅ 341 0 CONHC₃H₇ 342 1 CH₂SO₂(CH₂)₂OCH₃ 343 0 CON(CH₃)CH₂CH₂CN 344 0 CH₂OCH₂CH═CH₂ 345 0 CH₂N(C₂H₅)C(O)(CH₂)₂CH═CH₂ 346 0 CH₂N(CH₃)SO₂C₂H₅ 347 0 CH₂N(CH₃)COCH₃ 348 0 CH₂NHCO₂CH₂CH═CH₂ 349 0 CH₂SCH₃ 350 0 CO₂H 351 0 CH₂NHCO₂CH₂CH(CH₃)₂ 352 0 CH₂N(CH₃)₂

TABLE 3c

Physical m R² properties 353 0 CO₂H m.p. 143-144° C. 354 0 CH₂SC₂H₅ 355 0 CH₂N(CH₃)COC₂H₅ 356 0 CH₂OC(O)CH₃ 357 0 CH₂N(CH₃)CO₂CH₂CH═CH₂ 358 1 CH₂SO₂CH₃ 359 0 CON(CH₃)C₂H₅ 360 0 CH₂N(CH₃)-cyclo-C₆H₁₁ 361 0 CH₂OCH₂CF₃ 362 CH₂SCH₃ oil 363 0 CH₂NHSO₂CH₂CF₃ 364 0 CH₂SO(CH₂)₂CH₃ 365 0 CO₂CH₃ 366 0

367 0 CH₂N(CH₃)CO(CH₂)₂SCH₃ 368 0 CH₂S(CH₂)₃OH 369 1 CH₂SO₂CH₂CF₃ 370 0 CH₂N(CH₂)₅ 370a 0 CH₂N(CH₃)CO₂C₂H₅ 372 0 CH₂CO₂CH₂Ph 373 0 CH₂N(CH₃)COCH₂OCH₃ 374 0 CH₂OCH₂CF₃ 375 0 CH₂(O(CH₂)₂)₂OCH₃ 376 0 CO₂-cyclo-C₃H₅ 377 0 CONHCH₂CN 378 0 CH₂SCH₂-2-pyridyl 379 0 CH₂N(CH₃)CO-cyclo-C₃H₅ 380 0 CH₂NHCH₂CF₃ 381 0 CONHCH₂CH═CH₂ 382 0 CH₂NHCOCH₂SCH₃ 383 0 CH₂CO₂H 384 0 CH₂N(CH₃)SO₂CH₃ 385 0 CH₂OCH₂C≡CH 386 0 CH₂OC(O)N(CH₃)₂ 387 0 CH₂SCH(CH₂)₅ 387a 0 CONHC(CH₃)₃ 388 0 CH₂OCH(CH₂)₃ 389 0 CH₂N(CH₃)(CH₂)₂N(CH₃)₂ 390 0 CH₂OC(O)CH₂CN 391 0

392 0 CH₂OC(O)CH(CH₃)₂ 393 0 CON(CH₃)-n-C₃H₇ 394 0 CON(CH₃)₂ m.p. 62-63° C. 395 0 CH₂I 396 0 CONHCH₃ 397 0 CH₂N(CH₃)C(O)SCH₃ 398 0 CH₂N(CH₃)CO₂CH₂CH(CH₃)₂ 399 0 CONHC₂H₅ 400 0 CH₂SCH₂CH(CH₃)₂ 401 0 CO₂C(CH₃)₃ 402 0 CH₂OC(O)CH₂CH(CH₃)₂ 403 0 CON(CH₃)CH₂CH═CH₂ 404 0 CH₂O(CH₂)₂CH₃ 405 0 CH₂SO₂CH₂-2-furfuryl 406 0 CON(CH₂)₅ 407 0 CH₂SCH₂-2-furfuryl 408 0 CON(CH₃)CH(OCH₃)₂ 409 0 CH₂SOCH₃ 410 0 CH₂SCH₂-2-pyrimidyl 411 0 CH₂OC(O)CH═CH₂ 412 0 CH₂NH-cyclo-C₃H₅ 413 0 CONHCH(CH₃)₂ 414 0 CH₂OC(O)CH₂CH₂Si(CH₃)₃ 415 0

416 0 CH₂OCH₂-cyclo-C₃H₅ 417 0 CH₂OC₂H₅ 418 0 CH₂NHC(O)SPh 419 0 CON(CH₂)₃ 420 1 CH₂SO₂CH₂-2-furfuryl 421 0 CH₂OC(O)C(CH₃)₃ 422 0 CH₂SO₂(CH₂)₂CH₃ 423 0 CH₂CON(CH₃)₂ m.p. 113-114° C. 424 0

425 0 CONHCH₂-cyclo-C₃H₅ 426 0 CH₂N(C₂H₅)COCH₃ 427 0 CH₂N(CH₃)COCH₂-cyclo-C₅H₉ 428 0 CH₂OCH₂CH(CH₃)₂ 429 0 CH₂OCO₂CH₃ 430 0 CON(CH₃)OCH₃ 431 0 CH₂NHCH(CH₃)₂ 432 0 CH₂SOCH₂CF₃ 433 0 CH₂NHCO₂CH₂CH₂Cl 434 0 CH₂N(CH₃)CH(CH₃)₂ 435 0 CON(CH₃)CH₂-cyclo-C₃H₅ 436 0 CH₂NHC(O)S(CH₂)₂CH₃ 437 0 CON(CH₃)CH₂CN 439 0 CH₂NH₂ 440 0

441 0 CH₂NH(CH₂)₂OCH₃ 442 0 CH₂N(CH₃)SO₂CH₂CF₃ 443 0 CH₂N(C₂H₅)₂ 444 0 CH₂SCH₂CH═CH₂ 445 0 CON(CH₂)₄ 446 0 CH₂SO(CH₂)₂OCH₃ 447 0 CH₂NHSO₂C₂H₅ 448 0 CO₂CH₂Ph 449 0 CH₂NHCOCH(CH₃)₂ 450 0 CH₂OC(O)CH₂CO₂CH₃ 451 0 CONH(CH₂)₂OCH₃ 452 0 CH₂OC(O)C₂H₅ 453 0 CH₂OCO₂CH₂CH(CH₃)₂ 454 0 CH₂N(CH₃)CH₂CO₂CH₃ 455 0 CH₂NHC₂H₅ 456 0 CH₂NHCOCH₃ 457 0 CH₂OH m.p. 70-71 ° C. 458 0 CH₂NHCH₂C≡CH 459 0 CH₂N(CH₃)COCH₃ 460 0 CH₂NHCH₃ 461 0 CH₂N(CH₃)CO₂CH₂CH₂Cl 462 0 CH₂N(CH₃)SO₂CH₂CF₃ 463 0 CH₂NHSO₂CH(CH₃)₂ 464 0

465 0 CH₂NHCO(CH₂)₂SCH₃ 466 0 CH₂NHCOCH₂-cyclo-C₅H₉ 467 0 CH₂NH(CH₂)₃CH₃ 468 0 CH₂O(CH₂)₃CH₃ 469 0 CH₂Cl oil 470 0 CH₂CO₂C₂H₅ 471 0 CONHC₃H₇ 472 0 CON(CH₃)CH₂CH₂CN 473 0 CH₂OCH₂CH═CH₂ 474 0 CH₂N(CH₃)SO₂C₂H₅ 475 0 CH₂N(CH₃)COCH₃ 476 0 CH₂CO₂CH₃ 477 0 CONHCH₂CF₃ 478 0 CH₂NHCO(CH₂)₂CH═CH₂ 479 0 CH₂CO₂C(CH₃)₃ 480 0 CH₂NHCO₂CH₂CH═CH₂ 481 0 CH₂NHCO-cyclo-C₄H₇ 482 0 CH₂NHCO₂CH₂CH(CH₃)₂ 483 0 CH₂CN 484 0 CON(CH₃)(CH₂)₂CH(CH₃)₂ 485 0 CH₂N(CH₃)C(O)N(CH₃)₂ 486 0 CH₂NHC(O)SCH₃ 487 0 CH₂N(CH₃)COCH₂SCH₃ 488 0 CH₂N(C₂H₅)C(O)(CH₂)₂CH═CH₂ 489 0 CH₂NHCO₂C₂H₅ 490 0 CH₂NHCO-cyclo-C₃H₅ 491 1 CH₂SO₂(CH₂)₂OCH₃ 492 0 CH₂SCH₂CH₂OH 493 0 CON(CH₃)CH₂CH₂OC(O)CH₃ 494 0 CH₂OC(O)CH₂CH₂CH₃ 495 0 CH₂CO₂-cyclo-C₃H₅ 496 0 CH₂S(CH₂)₂CH₃ 497 0 CH₂SCH(CH₂)₄ 498 0 CH₂SO₂CH₂CF₃ 499 0 CH₂SO₂(CH₂)₂OCH₃ 500 0 CH₂N(CH₃)CH₂CN 501 0 CH₂N(C₂H₅)CH₂CH═CH₂ 502 0

503 0 CH₂N(C₂H₅)CH₂CH₂OCH═CH₂ 504 0 CH₂N(CH₃)CO-cyclo-C₄H₇ 505 0 CH₂S(CH₂)₂N(CH₃)₂ 506 0 CH₂SOCH₂-2-furfuryl 507 0 CON(CH₃)-n-C₄H₉ 508 0 CH₂OC(O)CO₂CH₃ 509 0 CH₂F 510 0

511 0 CON(CH₃)CH₂CH₂N(CH₃)₂ 512 0 CONH(CH₂)₃CH₃ 513 0

514 0 CH₂NHCOCH═C(H)CH₃ 515 0 CH₂SC(CH₃)₃ 516 0 CH₂O(CH₂)₂OCH₃ 517 0 CH₂Br 518 0 CH₂N(CH₃)C(CH₃)₃ 519 0 CH₂N(CH₃)COCH(CH₃)₂ 520 0

521 0 CONHCH₂C≡CH 522 0 CH₂NHC(O)N(CH₃)₂ 523 1 CH₂SO₂(CH₂)₂CH₃ 524 0 CH₂OCH₃ 525 0 CH₂SCH₂CH₂OCH₃ 526 0 CH₂SO₂CH₃ 527 0 CH₂NHCOCH₂CH(CH₃)₂ 528 0 CH₂SCH₂-cyclo-C₃H₅

TABLE 3d

Physical m R² properties 529 0 CONHCH₂CF₃ 530 0 CH₂NHCH₃ 531 0

532 0 CH₂NHC(O)N(CH₃)₂ 533 0 CH₂N(CH₃)CO₂C₂H₅ 534 0 CH₂NHCO₂CH₂CH═CH₂ 535 0 CONHC₃H₇ 536 0 CH₂NHC(O)SCH₃ 537 0 CH₂CO₂C(CH₃)₃ 538 0 CH₂N(CH₃)COCH₃ 539 0 CON(CH₃)CH₂CH₂N(CH₃)₂ 540 0 CH₂OCH₂CF₃ 541 0 CH₂N(CH₃)SO₂C₂H₅ 542 0 CH₂OC(O)CH₂CN 543 0 CH₂CO₂CH₂Ph 544 0 CH₂N(C₂H₅)COCH₃ 545 0 CON(CH₃)C₂H₅ 546 0 CH₂OCH₂CF₃ 547 0 CH₂NHSO₂CH₂CF₃ 548 0 CH₂OC(O)CH₂CH₂CH₃ 549 0 CH₂NHCOCH═C(H)CH₃ 550 0 CH₂N(C₂H₅)₂ 551 0 CON(CH₃)(CH₂)₂CH(CH₃)₂ 552 0 CONHC(CH₃)₃ 553 0 CO₂CH₃ crystalline 554 0 CH₂N(CH₃)SO₂CH₂CF₃ 555 0 CH₂N(CH₃)CO-cyclo-C₃H₅ 556 0 CH₂NHSO₂CH(CH₃)₂ 557 0

558 0 CH₂SO₂(CH₂)₂CH3 559 0 CH₂NHCH₂CF₃ 560 0 CH₂SCH₂CH₂OCH₃ 561 0 CH₂SC₂H₅ 562 0 CH₂N(CH₃)CO₂CH₂CH═CH₂ 563 0 CH₂NH(CH₂)₃CH₃ 564 0 CH₂N(CH₃)CO₂CH₂CH₂Cl 565 0 CH₂OC(O)CH═CH₂ 566 0 CH₂NH-cyclo-C₃H₅ 567 0 CH₂NHCO₂CH₂CH(CH₃)₂ 568 0 CH₂CO₂C₂H₅ 569 0 CH₂Cl 570 0 CH₂N(CH₃)COC₂H₅ 571 0 CH₂SO(CH₂)₂OCH₃ 572 0 CH₂O(CH₂)₃CH₃ 573 0 CH₂N(CH₃)CH₂CO₂CH₃ 574 0 CH₂OC(O)CH₂CH₂Si(CH₃)₃ 575 0 CH₂N(CH₃)COCH₃ 576 0 CH₂N(CH₃)C(O)N(CH₃)₂ 577 0 CH₂N(CH₃)COCH₂-cyclo-C₅H₉ 578 0 CH₂N(CH₃)CH₂CN 579 0 CH₂OC(O)CH₂CO₂CH₃ 580 0 CO₂C(CH₃)₃ 581 0 CONHCH₃ 582 0 CH₂NHCO(CH₂)₂SCH₃ 583 0

584 0 CH₂S(CH₂)₃OH 585 0 CH₂N(CH₂)₅ 586 0 CON(CH₃)CH₂CH₂CN 587 0 CO₂C₂H₅ 588 0 CH₂N(CH₃)(CH₂)₂N(CH₃)₂ 589 0

590 0 CON(CH₃)CH₂CH═CH₂ 591 0 CH₂NHCOCH₂-cyclo-C₅H₉ 592 0 CON(CH₂)₃ 593 0 CO₂-cyclo-C₃H₅ 594 0 CONHCH₂-cyclo-C₃H₅ 595 0 CH₂N(CH₃)C(O)SCH₃ 596 0 CH₂N(CH₃)CH(CH₃)₂ 597 0 CH₂N(CH₃)SO₂CH₂CF₃ 598 0 CH₂SCH₂CH(CH₃)₂ 599 0 CONHCH(CH₃)₂ 600 0 CH₂OCH₂CH═CH₂ 601 1 CH₂SO₂(CH₂)₂OCH₃ 602 1 CH₂SO₂CH₂-2-furfuryl 603 0 CH₂SO(CH₂)₂CH₃ 604 0 CON(CH₂)₄ 605 0 CH₂OCH(CH₂)₃ 606 0 CH₂OCH₂CH(CH₃)₂ 607 0 CONH(CH₂)₃CH₃ 608 0 CON(CH₃)CH₂-cyclo-C₃H₅ 609 0 CH₂N(C₂H₅)CH₂CH═CH₂ 610 1 CH₂SO₂(CH₂)₂CH₃ 611 0 CONH(CH₂)₂OCH₃ 612 0 CH₂S(CH₂)₂N(CH₃)₂ 613 0 CH₂SO₂CH₂CF₃ 614 0 CH₂NHCO-cyclo-C₃H₅ 615 0 CH₂OC(O)C(CH₃)₃ 616 0 CON(CH₃)₂ m.p. 91-92° C. 617 0 CH₂NH(CH₂)₂OCH₃ 618 0 CO₂CH₂Ph 619 0 CH₂O(CH₂)₂OCH₃ 620 0 CH₂SOCH₃ 621 0 CH₂SCH(CH₂)₄ 622 0 CH₂NHCO₂CH₂CH₂Cl 623 0 CH₂N(CH₃)COCH₂OCH₃ 624 0 CH₂N(CH₃)C(CH₃)₃ 625 0 CH₂CO₂H 626 0 CH₂SCH₂-2-furfuryl 627 0 CH₂OCH₃ 628 0 CH₂SO₂CH₂-2-furfuryl 629 0 CH₂SCH₂CH═CH₂ 630 0 CH₂Br 631 0 CH₂NHC(O)SPh 632 0

633 0 CON(CH₃)OCH₃ 634 0 CH₂(O(CH₂)₂)₂OCH₃ 635 0 CH₂NHCO(CH₂)₂CH═CH₂ 636 0 CONHCH₂CN 637 0 CH₂NHCH₂C≡CH 638 0 CH₂I 639 0 CH₂OC(O)CH(CH₃)₂ 640 0 CH₂NHCO₂C₂H₅ 641 0 CH₂S(CH₂)₂CH₃ 642 0 CH₂N(CH₃)COCH(CH₃)₂ 643 0 CON(CH₂)₅ 644 0

645 0 CONHCH₂C≡CH 646 0 CH₂CON(CH₃)₂ 647 0 CH₂SOCH₂CF₃ 648 0 CH₂N(CH₃)CO₂CH₂CH(CH₃)₂ 649 0 CH₂NH₂ 650 0 CH₂SC(CH₃)₃ 651 0 CH₂SCH₂-2-pyridyl 652 0 CH₂OCH₂C≡CH 653 0 CH₂OC(O)CH₂CH(CH₃)₂ 654 0 CH₂SCH₂CH₂OH 655 0 CH₂SOCH₂-2-furfuryl 656 0 CH₂OH crystalline 657 0 CH₂CO₂CH₃ 658 0

659 0 CON(CH₃)CH₂CN 660 0 CH₂SCH₂-2-pyrimidyl 661 0 CH₂OCH₂-cyclo-C₃H₅ 662 0 CON(CH₃)-n-C₃H₇ 663 0 CH₂OC(O)CH₃ 664 0 CH₂NHSO₂C₂H₅ 665 0 CON(CH₃)-n-C₄H₉ 666 0 CH₂N(CH₃)-cyclo-C₆H₁₁ 667 0 CH₂OC(O)C₂H₅ 668 0 CON(CH₃)CH(OCH₃)₂ 669 0 CH₂NHC(O)S(CH₂)₂CH₃ 670 0 CH₂SO₂CH₃ 671 0 CH₂NHCH(CH₃)₂ 672 0 CH₂NHCOCH(CH₃)₂ 673 0 CH₂N(CH₃)COCH₂SCH₃ 674 0 CH₂CO₂-cyclo-C₃H₅ 675 0 CH₂N(CH₃)CO-cyclo-C₄H₇ 676 0 CH₂OC(O)N(CH₃)₂ 677 0

678 0

679 0 CH₂NHCOCH₃ 680 0 CON(CH₃)CH₂CH₂OC(O)CH₃ 681 0 CH₂N(CH₃)SO₂CH₃ 682 0 CH₂NHC₂H₅ 683 0 CONHCH₂CH═CH₂ 684 0 CH₂SO₂(CH₂)₂OCH₃ 685 0 CH₂N(C₂H₅)CH₂CH₂OCH═CH₂ 686 0 CH₂F 687 0 CH₂SCH(CH₂)₅ 688 0 CH₂NHCOCH₂SCH₃ 689 0 CH₂O(CH₂)₂CH₃ 690 0 CH₂OCO₂CH₂CH(CH₃)₂ 691 0 CH₂NHCO-cyclo-C₄H₇ 692 0 CH₂OCO₂CH₃ 693 0 CH₂NHCOCH₂CH(CH₃)₂ 694 1 CH₂SO₂CH₂CF₃ 695 1 CH₂SO₂CH₃ 697 0 CH₂OC₂H₅ 698 0 CH₂SCH₂-cyclo-C₃H₅ 699 0 CH₂N(C₂H₅)C(O)(CH₂)₂CH═CH₂ 700 0 CH₂N(CH₃)CO(CH₂)₂SCH₃ 701 0

702 0 CH₂OC(O)CO₂CH₃ 703 0 CH₂CN 704 0 CONHC₂H₅

TABLE 3e

Physical m R² properties 705 0 CONHCH₂CF₃ 706 0 CH₂N(CH₃)COCH₃ oil 707 0 CH₂NHSO₂CH₂CF₃ 708 0 CH₂NHSO₂CH(CH₃)₂ 709 0 CH₂OC(O)CH═CH₂ 710 0 CO₂C(CH₃)₃ 711 0 CON(CH₂)₃ 712 0 CH₂OCH(CH₂)₃ 713 0 CH₂NH(CH₂)₂OCH₃ 714 0 CH₂NHC(O)SPh 715 0 CH₂OC(O)CH(CH₃)₂ 716 0 CH₂OC(O)CH₂CH(CH₃)₂ 717 0 CH₂NHCOCH₂SCH₃ 718 CH₂OCH(CH₃)₂ oil 719 0 CH₂NHCH₃ oil 720 0 CON(CH₃)CH₂CH₂N(CH₃)₂ 721 0 CH₂OC(O)CH₂CH₂CH₃ 722 0

723 0 CH₂NH-cyclo-C₃H₅ 724 0 CH₂OC(O)CH₂CO₂CH₃ 725 0 CONHCH₃ 726 0 CH₂NHCOCH₂-cyclo-C₅H₉ 727 0 CON(CH₂)₄ 728 0 CON(CH₃)₂ m.p. 105-106° C. 729 0

730 0 CH₂S(CH₂)₂CH₃ 731 0 CH₂SCH₂-2-pyridyl 732 0 CON(CH₃)CH(OCH₃)₂ 733 0 CON(CH₃)CH₂CH₂OC(O)CH₃ 734 0 CH₂O(CH₂)₂CH₃ 735 0 CH₂NHCO-cyclo-C₄H₇ 736 0 CH₂N(C₂H₅)C(O)(CH₂)₂CH═CH₂ 737 0

738 0 CH₂OCH₂CF₃ 739 0 CH₂NHCOCH═C(H)CH₃ 740 0 CH₂SO₂(CH₂)₂CH3 741 0 CH₂NHCO₂CH₂CH(CH₃)₂ 742 0 CH₂NHCO(CH₂)₂SCH₃ 743 0 CON(CH₃)CH₂CH═CH₂ 744 0 CH₂SCH₂CF₃ oil 745 0 CH₂OC(O)C(CH₃)₃ 746 0 CON(CH₃)OCH₃ 747 0 CONHCH₂C≡CH 748 0 CH₂OH crystalline 749 0 CH₂OC(O)C₂H₅ 750 0 CH₂N(CH₃)SO₂CH₃ 751 0 CH₂OCO₂CH₂CH(CH₃)₂ 752 0 CH₂N(CH₃)CO(CH₂)₂SCH₃ 753 0 CH₂NHC(O)N(CH₃)₂ 754 0 CH₂N(CH₃)SO₂C₂H₅ 755 0 CH₂N(C₂H₅)₂ 756 0 CH₂NHCH₂CF₃ 757 0 CH₂N(CH₃)COC₂H₅ 758 0 CH₂N(CH₃)C(O)N(CH₃)₂ 759 0 CH₂N(CH₂)₅ 760 0 CO₂-cyclo-C₃H₅ 761 1 CH₂SO₂(CH₂)₂OCH₃ 762 0 CH₂OCH₂CH(CH₃)₂ 763 0 CH₂S(CH₂)₂N(CH₃)₂ 764 0 CO₂CH₂Ph 765 0 CH₂N(CH₃)C(CH₃)₃ 766 0 CH₂Br 767 0 CH₂NHCO₂C₂H₅ 768 0 CH₂SC(CH₃)₃ 769 0 CH₂OCH₂-cyclo-C₃H₅ 770 0 CH₂CO₂-cyclo-C₃H₅ 771 0 CH₂F 772 0 CH₂OCO₂CH₃ 773 0 CH₂OC₂H₅ oil 774 0 CH₂OC(O)CO₂CH₃ 775 0 CH₂N(CH₃)CO₂C₂H₅ 776 0 CH₂OC(O)CH₂CN 777 0 CON(CH₃)(CH₂)₂CH(CH₃)₂ 778 0 CH₂SCH₂CH₂OCH₃ 779 0 CH₂Cl oil 780 0 CH₂N(CH₃)COCH₂-cyclo-C₅H₉ 781 0 CH₂S(CH₂)₃OH 782 0 CH₂N(CH₃)C(O)SCH₃ 783 1 CH₂SO₂CH₂-2-furfuryl 784 0 CONH(CH₂)₃CH₃ 785 0 CH₂SO₂CH₂CF₃ 786 0 CH₂O(CH₂)₂OCH₃ 787 0 CH₂CO₂H 788 0 CH₂NHCO(CH₂)₂CH═CH₂ 789 0 CH₂OCH₂C≡CH 790 0 CH₂SCH₂CH₂OH 791 0 CON(CH₃)-n-C₃H₇ 792 0 CH₂NHC(O)S(CH₂)₂CH₃ 793 0 CH₂N(CH₃)COCH₂SCH₃ 794 0

795 0 CH₂SCH(CH₂)₅ 796 0 CH₂NHCOCH₂CH(CH₃)₂ 797 0 CH₂SCH₂-cyclo-C₃H₅ 798 0

799 0 CH₂SCH₂CH₂CH₃ oil 800 0 CH₂NHCO₂CH₂CH═CH₂ 801 0 CH₂CO₂CH₂Ph 802 0 CONHC(CH₃)₃ 803 0 CH₂SC₂H₅ 804 0 CH₂CO₂C₂H₅ 805 0

806 0

807 0 CH₂N(CH₃)CH(CH₃)₂ 808 0 CH₂SO(CH₂)₂CH₃ 809 0 CON(CH₃)CH₂-cyclo-C₃H₅ 810 0 CH₂NHCO-cyclo-C₃H₅ 811 0 CH₂SOCH₃ 812 0 CH₂SCH₂-2-furfuryl 813 0 CH₂(O(CH₂)₂)₂OCH₃ 814 0 CH₂I 815 0 CH₂CON(CH₃)₂ 816 0 CH₂CO₂CH₃ 817 0 CH₂OC(O)CH₃ 818 0 CH₂SO₂CH₃ 819 0

820 0 CH₂NHC₂H₅ 821 0 CH₂CN 822 0 CONHC₃H₇ 823 0 CH₂N(C₂H₅)COCH₃ 824 0 CO₂CH₃ crystalline 825 0 CH₂N(CH₃)CO₂CH₂CH═CH₂ 826 0 CH₂SO(CH₂)₂OCH₃ 827 0 CH₂N(CH₃)COCH₃ 828 0 CON(CH₃)CH₂CH₂CN 829 0 CONHCH₂-cyclo-C₃H₅ 830 0 CH₂OCH₂CH═CH₂ 831 0 CONH(CH₂)₂OCH₃ 832 0 CH₂N(CH₃)COCH₂OCH₃ 833 0 CH₂SCH₂CH═CH₂ 834 0 CH₂N(CH₃)COCH(CH₃)₂ 835 0 CH₂NH₂ 836 0 CH₂SCH₂-2-pyrimidyl 837 0 CH₂N(CH₃)-cyclo-C₆H₁₁ 838 0 CH₂NHCOCH(CH₃)₂ 839 0 CH₂N(CH₃)CO-cyclo-C₄H₇ 840 0 CH₂N(C₂H₅)CH₂CH₂OCH═CH₂ 841 0 CO₂H m.p. 188-189° C. 842 0 CH₂NHC(O)SCH₃ 843 0 CON(CH₃)C₂H₅ 844 0 CH₂N(CH₃)SO₂CH₂CF₃ 845 0 CH₂NH(CH₂)₃CH₃ 846 0 CH₂O(CH₂)₃CH₃ 847 0 CH₂OC(O)CH₂CH₂Si(CH₃)₃ 848 0 CO₂C₂H₅ crystalline 849 0 CONHCH(CH₃)₂ 850 1 CH₂SO₂(CH₂)₂CH₃ 851 0 CH₂NHCO₂CH₂CH₂Cl 852 0 CH₂SO₂CH₂-2-furfuryl 853 0 CONHCH₂CN 854 0 CON(CH₂)₅ 855 0 CH₂N(CH₃)CO₂CH₂CH(CH₃)₂ 856 0 CON(CH₃)CH₂CN 857 0 CON(CH₃)-n-C₄H₉ 858 0 CH₂SO₂(CH₂)₂OCH₃ 859 1 CH₂SO₂CH₃ 860 CH₂SCH₂CH(CH₃)₂ oil 861 0 CH₂CO₂C(CH₃)₃ 862 0 CH₂OCH₂CF₃ 863 0 CH₂N(CH₃)CO-cyclo-C₃H₅ oil 864 0 CH₂N(CH₃)CO₂CH₂CH₂Cl 865 0 CH₂N(CH₃)CH₂CO₂CH₃ 866 0 CH₂N(CH₃)(CH₂)₂N(CH₃)₂ 867 0 CH₂N(CH₃)SO₂CH₂CF₃ crystalline 868 0 CH₂N(C₂H₅)CH₂CH═CH₂ 869 0 CH₂SCH(CH₂)₄ 870 0 CH₂OCH₃ oil 871 0 CH₂NHCH₂C≡CH 872 0

873 0 CH₂SOCH₂CF₃ 874 0

875 0 CH₂NHSO₂C₂H₅ 876 0 CH₂NHCH(CH₃)₂ 877 0 CH₂OC(O)N(CH₃)₂ 878 0 CONHCH₂CH═CH₂ 879 1 CH₂SO₂CH₂CF₃ 880 0 CH₂SCH₃ oil 881 0 CONHC₂H₅ 882 0 CH₂SOCH₂-2-furfuryl 883 0 CH₂N(CH₃)CH₂CN 884 0 CH₂NHCOCH₃

B. FORMULATION EXAMPLES

a) A dusting powder is obtained by mixing 10 parts by weight of active compound and 90 parts by weight of talc, as inert substance, and comminuting the mixture in an impact mill.

b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of active compound, 65 parts by weight of kaolin-containing quartz, as the inert substance, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurinate, as wetting and dispersing agent, and grinding the mixture in a pinned disk mill.

c) A dispersion concentrate which is readily dispersible in water is prepared by mixing 40 parts by weight of active compound with 7 parts by weight of a sulfosuccinic monoester, 2 parts by weight of a sodium ligninsulfonate and 51 parts by weight of water and grinding the mixture to a fineness of below 5 microns in a grinding bead mill.

d) An emulsifiable concentrate can be prepared from 15 parts by weight of active compound, 75 parts by weight of cyclohexane, as the solvent, and 10 parts by weight of ethoxylated nonylphenol (10 EO), as the emulsifier.

e) Granules can be prepared from 2 to 15 parts by weight of active compound and an inert granule carrier material, such as attapulgite, pumice granules and/or quartz sand. A suspension of the wettable powder from Example b) having a solids content of 30% is expediently used, and this is sprayed onto the surface of attapulgite granules and the components are dried and mixed intimately. The weight content of the wettable powder is approximately 5% and that of the inert carrier material is approximately 95% of the finished granules.

C. BIOLOGICAL EXAMPLES Example 1

Germinated broad bean seeds (Vicia faba) with radicles were transferred into brown glass bottles filled with tap water and subsequently populated with approximately 100 black bean aphids (Aphis fabae). Plants and aphids were then dipped for 5 seconds into an aqueous solution of the formulated preparation to be examined. After the solution had dripped off, plants and animals were kept in a climatized chamber (16 hours of light/day, 25° C., 40-60% relative atmospheric humidity). After 3 and 6 days storage, the effect of the preparation on the aphids was determined. At a concentration of 300 ppm (based on the content of active compound), the preparations of Example Nos. 1/37, 1/78, 1/136, 1/94, 1/174, 1/14, 1/125, 1/187, 1/17, 1/84, 1/52, 1/82, 1/70, 3/74, 1/54, 1/81, 1/42, 3/161, 1/186 effected a mortality of 90-100% among the aphids. (The active compounds are numbered with the Table/No. in the table).

Example 2

The leaves of 12 rice plants having a stem length of 8 cm were dipped for 5 seconds into an aqueous solution of the formulated preparation to be examined. After the solution had dripped off, the rice plants treated in this manner were placed in a Petri dish and populated with approximately 20 larvae (L3 stage) of the rice leafhopper species Nilaparvata lugens. The Petri dish was closed and stored in a climatized chamber (16 hours of light/day, 25° C., 40-60% relative atmospheric humidity). After 6 days storage, the mortality among the leafhopper larvae was determined. At a concentration of 300 ppm (based on the content of active compound), the preparations of Example Nos. 1/53, 1/26, 1/164, 1/174, 1/82, 1/42 effected a mortality of 90-100%.

Example 3

Germinated broad bean seeds (Vicia faba) with radicles were transferred into brown glass bottles filled with tap water. Four milliliters of an aqueous solution of the formulated preparation to be examined were pipetted into the brown glass bottle. The broad bean was subsequently heavily populated with approximately 100 black bean aphids (Aphis fabae). Plants and animals were then stored in a climatized chamber (16 hours of light/day, 25° C., 40-60% relative atmospheric humidity). After 3 and 6 days storage, the root-systemic activity of the preparation on the aphids was determined. At a concentration of 30 ppm (based on the content of active compound), the preparations of Example Nos. 1/53, 1/26, 1/37, 1/78, 1/136, 1/56, 1/94, 1/174, 1/14, 1/187, 1/84, 1/52, 1/82, 1/70, 1/32, 3/74, 1/54, 1/81, 1/42, 3/227, 3/161 effected a mortality of 90-100% among the aphids by root-systemic action. 

What is claimed is:
 1. A 4-trifluoromethyl-3-oxazolyl compound of the formula (I)

wherein: m is 0 or 1; R¹ and R² are a) H, CH₃, —C₂H₅, —CH₂—CH₂—CH₃—, CH₂(CH₃)₂ or cyclopropyl or b) —CH₃, CH₂XR³, —CHY, —CO₂R⁴ or —CONR⁵R⁶, where in each case one of the radicals R¹, R² is one of the group a and the other is of the group b; X is O, S, SO, SO₂ or NR⁷; Y is O, BR₂, ((C₁-C₄)-alkoxy)₂, ((C₁-C₄)-alkylthio)₂, V—(CH₂)₂ or 3—V, where V=O, S, where an H atom is replaced or not replaced by (C₁-C₄) alkyl; R³ is R⁸, COR⁹, CO₂R¹⁰, CONR¹¹R¹² or, if X is O or NR⁷, is SO₂R¹³; R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³ are identical or different and are independently of one another H, (C₁-C₁₀)-alkyl, (C₂-C₁₀)-alkenyl, (C₂-C₁₀)-alkynyl, (C₃-C₈)-cycloalkyl, (C₄-C₈)-cycloalkenyl, (C₆-C₈)-cycloalkynyl aryl or heterocyclyl, where each of the eight last-mentioned groups is unsubstituted or mono-or polysubstituted, and where in each case R⁵ and R⁶ and R¹¹ and R¹² together are —(CH₂)₄—, —(CH₂)₅—, —(CH₂)₂—O—(CH₂)₂—or —(CH₂)₂—NR⁴—(CH₂)₂—; with the proviso, that the compounds in which R¹=CO₂C₂H₅ and R²=H, R¹=H and R²=CH₂NHC₆H₅, R¹=CH₃ and R²=CO₂H, R¹=CH₃ and R²=CO₂C₂H₅ R¹=CH₃ and R²=CON(CH₃)₂ R¹=CH(CH₃)₂ and R²=CO₂H, R¹=CH(CH₃)₂ and R² CO₂C₂H₅ are not included.
 2. A 4-trifluoromethyl-3-oxazolylpyridine as claimed in claim 1, wherein R¹ is H and R² is a radical of the group b.
 3. A 4-trifluoromethyl-3-oxazolylpyridine as claimed in claim 1, wherein R¹ is a radical of the group b and R² is H.
 4. A 4-trifluoromethyl-3-oxazolylpyridine as claimed in claim 1, wherein R¹ is a radical of the group a, with the exception of hydrogen, and R² is a radical of the group b.
 5. A process for preparing compounds of the formula (I) as claimed in claim 1, which comprises reacting compounds of formula (II) where R¹ and R² are as defined in the formula (I) in claim 1 with a dehydrating agent,


6. A composition having insecticidal, acaricidal or nematicidal action, comprising a mixture of at least one compound of the formula (I) as claimed in claim 1 with a carrier substance and optionally with a surface-active substance.
 7. A method for controlling harmful insects, acarids and nematodes, which comprises applying an effective amount of a compound as claimed in claim 1 to the site of the desired action.
 8. A method for controlling harmful insects, acarids and nematodes, which comprises applying an effective amount of a composition as claimed in claim 6 to the site of the desired action.
 9. The process according to claim 5, wherein the dehydrating agent is selected from the group consisting of inorganic acid chlorides, inorganic acids and anhydrides. 